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Selective Catalytic Oxidation of Ethanol to Acetic Acid on Dispersed Mo-V-Nb Mixed Oxides

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Selective Catalytic Oxidation of Ethanol to Acetic Acid on Dispersed Mo-V-Nb Mixed Oxides DOI: 10.1002/chem.200700579 Selective Catalytic Oxidation of Ethanol to Acetic Acid on Dispersed Mo-V-Nb Mixed Oxides Xuebing Li and Enrique Iglesia*[a] Abstract: The direct oxidation of etha- tion proceeds via acetaldehyde inter- netic and isotopic effects indicate that nol to acetic acid is catalyzed by multi- mediates that are converted to acetic CÀH bond activation in chemisorbed component metal oxides (Mo-V-NbOx) acid. Water increases acetic acid selec- ethoxide species limits acetaldehyde prepared by precipitation in the pres- tivity by inhibiting acetaldehyde syn- synthesis rates and overall rates of eth- ence of colloidal TiO2 thesis more strongly than its oxidation anol conversion to acetic acid. The (Mo0.61V0.31Nb0.08Ox/TiO2). Acetic acid to acetic acid, thus minimizing preva- VOx component in Mo-V-Nb is respon- synthesis rates and selectivities (~95% lent acetaldehyde concentrations and sible for the high reactivity of these even at 100% ethanol conversion) its intervening conversion to COx.Ki- materials. Mo and Nb oxide compo- were much higher than in previous re- nents increase the accessibility and re- ports. The presence of TiO during syn- ducibility of VO domains, while con- 2 Keywords: acetaldehyde · acetic x thesis led to more highly active surface currently decreasing the number of un- acid · ethanol · molybdenum · areas without detectable changes in the selective V-O-Ti linkages in VO do- oxidation · sustainable chemistry · x reactivity or selectivity of exposed mains dispersed on TiO . vanadium 2 active oxide surfaces. Ethanol oxida- Introduction to producing chemicals, such as acetaldehyde and acetic acid, currently produced from ethane, ethene, or methanol. The conversion of alcohols to aldehydes, ketones, and car- Pd-based catalysts convert ethanol–O2 reactants to acetic boxylic acids by using stoichiometric oxidants (e.g., CrVI[1] acid, but with low reaction rates and modest selectivities and MnVII species[2]) leads to toxic waste by-products. Cata- (433 K, 70–90% acetic acid selectivity; 0.2 g-acetic acid g- À1 À1 [7] lytic processes using O2 or air as stoichiometric oxidants catalyst h ). Au clusters dispersed on MgAl2O4 convert minimize the cost and environmental impact of these chemi- aqueous ethanol solutions to acetic acid at ~453 K and [3] [8] cal processes. Specifically, inorganic solids, easily separated 0.6 MPa O2 pressure with yields of up to 90 %. Reducible [9] from organic reactants and products, and gas-phase process- oxides (e.g., Sn-MoOx ) also catalyze this reaction (< 60% es that avoid solid–liquid separations and use packed-bed acetic acid selectivity) at 423–573 K. A catalyst with VOx as reactors, would improve process efficiency. Inorganic cata- the active component (VOx/TiO2/clay) exhibited the best lysts for the oxidation of alcohols to aldehydes, ketones, and catalytic results for the oxidation of ethanol to acetic acid carboxylic acids typically consist of dispersed clusters of (97% acetic acid selectivity at 92% ethanol conversion).[10] noble metals and their oxides (e.g., Pt,[4] Pd,[5] Ru[6]). A summary of previous reports is included in Table 1. Ethanol has emerged as a fuel and a chemical feedstock Multicomponent inorganic oxides containing V and Mo available from biomass and could provide alternative routes catalyze reactions of O2 with alkanes to form alkenes and [11] acids; they also catalyze ethanol–O2 reactions, but with low acetic acid productivities (0.02 g-acetic acid g-cata- À1 À1 [12] [a]Dr. X. Li, Prof. Dr. E. Iglesia lyst h ) and modest selectivities (<70%). Department of Chemical Engineering We have recently found that mixed Mo-V-Nb oxides pre- University of California at Berkeley cipitated in the presence of TiO2 colloidal suspensions (P25, Berkeley, CA 94720 (USA) Degussa) give unprecedented acetic acid productivities and Fax : (+1)510-642-4778 E-mail: [email protected] very high selectivities for the catalytic oxidation of ethane [13] Supporting information for this article is available on the WWW and ethene by using O2. These experiments showed that under http://www.chemistry.org or from the author. acetic acid synthesis rates are controlled by elementary 9324 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2007, 13, 9324 – 9330 FULL PAPER Table 1. Summary of previous publications describing ethanol oxidation to acetic acid. Mo0.61V0.31Nb0.08Ox (0.13 g g-cat- À1 À1 Catalyst T[K]Ethanol Selectivity [%] Synthesis alyst h ), but the two synthe- conv[%]CH 3- CH3- CH3CO- COx rate sis protocols gave similar acetic CHO COOH OC2H5 [g g-cata- acid selectivities (Table 2). lystÀ1 hÀ1] Dispersing Mo0.61V0.31Nb0.08Ox [a] = Pd-Te-Zn/SiO2 Pd:0.86 % Te/Pd 0.9 Zn/ 433 90 1.4 92 3 3.1 0.244 structures onto TiO colloidal Pd= 0.1 ref. [7] 2 [b] suspensions led to higher total Au/MgAl2O4 ref. [8]453 97 – 85 – 15 0.90 2 À1 Sn-Mo oxide [c] ref. [9]548 100 20 60 1 19 0.55 surface areas (34 m g ; from [d] VOx/TiO2/clay ref. [10]473 92 – 97 – 3 0.19 N2 physisorption measurements [e] Mo16V5.6Nb0.5Sb0.3Ca0.3 ref. [12]528 98 0 66 0 20 0.022 at its normal boiling point) than = = [a]C 2H5OH:O2 :H2O:N2 2.5:6.25:25:66.5; Ptot 0.8 MPa. [b]150 mg catalyst, 1 wt% of metal, 10 mL of for bulk Mo0.61V0.31Nb0.08Ox = = 2 À1 5 wt% aqueous ethanol, 3 MPa total pressure, reaction for 4 h. [c]C 2H5OH:O2 :H2O:N2 3:24:13:73; Ptot (7.8 m g ) and apparently also 0.1 MPa. [d]C 2H5OH:O2:H2O:N2 =2.5:3:5:89.5; Ptot = 0.17 MPa. [e]C 2H5OH:O2 :H2O:N2 =2:6:6:86; Ptot = 0.7 MPa. to a larger number of accessible active sites. It is not possible to determine the fraction of acces- steps involving activation of CÀH bonds in ethane, followed sible surfaces consisting of Mo0.61V0.31Nb0.08Ox and uncovered by hydrogen abstraction to form ethene and acetaldehyde; TiO2 directly from the unselective physisorption of N2.We the acetaldehyde is then readily converted to acetic acid on have therefore used CO2 chemisorption at 313 K to measure Mo-V-Nb mixed oxides. The use of ethanol as a reactant, the fraction of the total surface area consisting of exposed [14] which we report here, circumvents these kinetic hurdles by TiO2. These data show that about 82% of the TiO2 sur- providing reactants with more facile oxidative dehydrogena- face was covered by Mo0.61V0.31Nb0.08Ox during precipitation tion routes to acetaldehyde than ethane or ethene reactants. of these active structures. From these data, we estimate the The process and catalysts reported here exploit the remark- surface area of active Mo0.61V0.31Nb0.08Ox components in this able reactivity of these dispersed oxides in the conversion of sample to be 28 m2 gÀ1, whereas the surface area of bulk 2 À1 acetaldehyde to acetic acid by using O2 and H2O. The dis- Mo0.61V0.31Nb0.08Ox powders is 7.8 m g . Areal acetic acid persed oxides described here as supported or unsupported synthesis rates (normalized by these active surface areas) oxides give 95% acetic acid selectivities and unprecedented then become 1610À8 and 7.710À8 molmÀ2 sÀ1 on catalyst productivities in a single-stage gas-phase ethanol ox- Mo0.61V0.31Nb0.08Ox/TiO2 and Mo0.61V0.31Nb0.08Ox, respectively. idation process at modest reaction temperatures (~500 K). These comparable areal rates, and the similar selectivities in these two samples, indicate that the higher reaction rates (per mass of active component) measured on TiO2-contain- Results and Discussion ing catalysts reflect a higher dispersion of active structures when such structures are precipitated in the presence of col- Rates and selectivities were measured at 473–533 K by using loidal TiO2. The slightly higher areal rate measured on the C2H5OH (32 kPa) and O2 (107 kPa). H2O (0–640 kPa) was supported sample reflects a slightly higher catalyst tempera- added because it increases acetic acid selectivity.[9] Helium ture, caused by higher local bed temperatures on such (1130 kPa) was used to dilute reactants and avoid explosive highly active catalysts. The temperature of the mixtures. Mo0.61V0.31Nb0.08Ox/TiO2, prepared by precipitation Mo0.61V0.31Nb0.08Ox/TiO2 bed was about 10 K higher than for of active components in the presence of colloidal suspen- the unsupported Mo0.61V0.31Nb0.08Ox sample for the same [13] sions of TiO2 (24 wt% active components), gave more heater temperature. than 90% acetic acid selectivities at complete ethanol con- Primary acetaldehyde products were detected at low etha- version (Table 2). Acetic acid synthesis rates (>1.0 g g-cata- nol conversions, but their concentration decreased with in- lystÀ1 hÀ1) were much higher than on unsupported creasing residence time (Figure 1), because of the role of acetaldehyde as an intermedi- ate in acetic acid synthesis Table 2. Oxidation of ethanol to acetic acid on multicomponent metal oxide. [a] (Scheme 1), evidenced by the Catalyst T[K]Ethanol Selectivity[%] Synthesis high acetic acid selectivity (95% at 100% acetaldehyde conv[%]CH 3- CH3- CH3CO- COx rate À1 À1 CHO COOH OC2H5 [g g-catalyst h ] conversion) in the oxidation of 24% Mo0.61V0.31Nb0.08Ox/TiO2 481 78 1.7 85 11 2.6 1.04 acetaldehyde at 473 K. Esterifi- 24% Mo0.61V0.31Nb0.08Ox/TiO2 510 100 0.04 95 0.5 4 1.16 cation of acetic acid with etha- 24% Mo0.61V0.31Nb0.08Ox/TiO2 533 100 0.05 92 0.01 6 1.12 nol led to small amounts of Mo V Nb O 473 57 4 75 17 3 0.13 0.61 0.31 0.08 x ethyl acetate; these equilibri- VOx/TiO 483 100 14 67 0.1 19 0.81 2 um-limited reactions are fa- MoOx/TiO2 473 17 94 1.5 0.7 3 0.003 MoOx-VOx/TiO2 481 100 26 58 0.5 16 0.71 vored at intermediate conver- sions, but are reversed as con- [a]Reaction conditions: partial pressure: ethanol: 32 kPa; O 2 : 107 kPa; H2O: 320 kPa, He: 1130 kPa and N2 : 11 kPa; total pressure: 1.6 MPa.
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