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Journal of Catalysis 281 (2011) 21–29

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Journal of Catalysis 281 (2011) 21–29 Journal of Catalysis 281 (2011) 21–29 Contents lists available at ScienceDirect Journal of Catalysis journal homepage: www.elsevier.com/locate/jcat Bifunctional transalkylation and hydrodeoxygenation of anisole over a Pt/HBeta catalyst ⇑ Xinli Zhu, Lance L. Lobban, Richard G. Mallinson, Daniel E. Resasco Center for Biomass Refining, School of Chemical, Biological, and Materials Engineering, The University of Oklahoma, Norman, OK 73019, USA article info abstract Article history: The catalytic conversion of anisole (methoxybenzene), a phenolic model compound representing a ther- Received 1 December 2010 mal conversion product of biomass lignin, to gasoline-range molecules has been investigated over a Revised 20 March 2011 bifunctional Pt/HBeta catalyst at 400 °C and atmospheric pressure. The product distribution obtained Accepted 30 March 2011 on the bifunctional catalyst was compared with those obtained on monofunctional catalysts (HBeta Available online 19 May 2011 and Pt/SiO2). This comparison indicates that the acidic function (HBeta) catalyzes the methyl transfer reaction (transalkylation) from methoxyl to the phenolic ring, yielding phenol, cresols, and xylenols as Keywords: the major products. The metal function catalyzes demethylation, hydrodeoxygenation, and hydrogena- Bifunctional hydrodeoxygenation tion in sequence, resulting in phenol, benzene, and cyclohexane. On the bifunctional catalyst, both methyl Phenolic compound Pt/HBeta transfer and hydrodeoxygenation are achieved at significantly higher rates than over the monofunctional Anisole catalysts, leading to the formation of benzene, toluene, and xylenes with lower hydrogen consumption Lignin and a significant reduction in carbon losses, in comparison with the metal function alone. In addition, Hydrogenation on the bifunctional Pt/HBeta, the rate of deactivation and coke deposition are moderately reduced. Hydrogenolysis Ó 2011 Elsevier Inc. All rights reserved. 1. Introduction catalysts can effectively reduce the oxygen content of phenolics in the bio-oil [6–21]. However, this type of processing results in Production of liquid hydrocarbon fuels from abundant lignocel- a significant loss of liquid yield, requires high hydrogen consump- lulosic biomass is being considered as a sustainable energy process. tion, and produces a sulfur containing stream. Zeolite upgrading Upgrading bio-oil derived from biomass via fast pyrolysis into (including hydrocracking) is operated at atmospheric pressure transportation fuels is an important step to accomplish this pro- and high temperatures (300–600 °C) with lower hydrogen con- cess. Lignin is a biopolymer formed from three main monomers: sumption [22–28]. Though zeolites are effective in conversion of coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. In contrast small oxygenates (such as aldehydes and ketones) through acid to cellulose and hemicellulose, from which thermal processing catalyzed reactions [22,29–31], their capability for deoxygenation produces high concentrations of relatively small oxygenates, lignin of phenolics is limited [23–28]. Increasing attention has been paid breaks down the polymer leading to high concentrations of pheno- to low temperature (<200 °C) and high pressure (3–5 MPa) hydro- lic molecules (phenol, guaiacol, syringol and their derivatives, see genation processes [32–36]. Full hydrogenation of the phenolic Scheme 1). Therefore, phenolic compounds represent a significant ring over metal sites followed by dehydration and re-hydrogena- fraction of the biomass pyrolysis bio-oil [1–4] and remain a chal- tion yields aliphatic hydrocarbons. It is evident that the hydrogen lenge for upgrading [3]. While building up the carbon chain is nec- consumption is high in this process and the products are not as essary for small oxygenates conversion, most phenolics are already valuable for gasoline blending. Minimizing carbon loss and also in the gasoline range, but they require a deoxygenation process hydrogen consumption (i.e. improving hydrogen efficiency [37]) that should preserve the carbon number within the range of gaso- are important parameters for the incorporation of biomass-derived line. As previously proposed [5], model compound studies are of liquids in refineries. Therefore, while the addition of aromatics to crucial importance to establish the conditions for conversion of the gasoline and diesel fuel pools will still be limited by technical phenolic-rich streams. and legislative caps, production of aromatics from the lignin frac- Hydrotreating and zeolite upgrading are the two main ap- tion of biomass is probably the most economically favorable pro- proaches for bio-oil conversion, and have been and are being inten- cess. Also, aromatics are important building blocks in sively studied. High temperature (250–400 °C) and high pressure petrochemical industry, and replacing their source from fossil to (3–5 MPa) hydrotreating of bio-oil over sulfided CoMo or NiMo renewable sources is certainly advantageous. As shown in Scheme 1, the hydroxyl (–OH) and methoxyl ⇑ Corresponding author. Fax: +1 405 325 5813. (–OCH3) are the major functional groups of lignin derived E-mail address: [email protected] (D.E. Resasco). phenolics. In previous work, it has been shown that the methyl 0021-9517/$ - see front matter Ó 2011 Elsevier Inc. All rights reserved. doi:10.1016/j.jcat.2011.03.030 22 X. Zhu et al. / Journal of Catalysis 281 (2011) 21–29 OH OH OH OH OH Phenols CH3 (CH3)2 Phenol Cresols Xylenols Catechol OCH3 OCH3 Anisoles CH3 Anisole Methylanisoles OH OH OH OH OH OCH3 OCH3 OCH3 OCH3 OCH3 Guaiacols CH2CH=CH2 CH=CHCH3 CH2COCH3 CHO Guaiacol Eugenol Isoeugenol 4-Acetonylguaiacol Vanillin OH OH H3CO OCH3 H3CO OCH3 Syringols CH2CH=CH2 Syringol 4-Allylsyringol Scheme 1. Structure of phenolic compounds. in the methoxyl of phenolics could be transferred to the aromatic The morphology of HBeta zeolite was studied by scanning elec- ring through acid catalyzed transalkylation reactions over HZSM- tronic microscopy (SEM) on a Jeol JSM-880 electron microscope, 5; while the hydroxyl appears to be inert under the same reaction equipped with energy dispersive X-ray analysis. Powder X-ray dif- conditions [28]. In this work, high temperature and low (atmo- fraction (XRD) patterns of the catalyst samples were obtained on a spheric) pressure operation for deoxygenation of phenolics over a Bruker D8 Discover diffractometer. The acid density of the HBeta bifunctional metal/zeolite catalyst are demonstrated. Moreover, zeolite was determined by temperature programmed desorption this deoxygenation is accomplished with low carbon loss in the (TPD) of isopropylamine (IPA) [38,39] following the procedure de- form of methane and low hydrogen consumption by phenolic ring scribed previously [30]. The dispersion of Pt was estimated by dy- hydrogenation. Anisole (methoxybenzene) has been chosen as a namic pulse CO adsorption. Catalyst samples were reduced at model compound of phenolics because (1) anisole contains an iso- 300 °C by flowing H2 for 1 h, and the temperature was held at lated methoxyl, one of the major functional groups of the lignin 300 °C for another 0.5 h in flowing He to desorb the adsorbed H2. phenolics; (2) the analysis of product distribution is relatively sim- After the sample was cooled down to room temperature in He, ple, i.e., after removal of the methyl from the methoxy group, the 100 lL of 5% CO/He gas mixture was pulsed onto the sample until hydroxyl group remains in the original molecule, while the source saturation of the surface of the catalyst was reached. The CO con- of any methyl transferred to another molecule can be accounted sumption was monitored by a thermal conductivity detector (TCD, for; and (3) anisole is liquid at room temperature, no solvent is SRI 310C GC). A CO/Pt stoichiometry of 1/1 was used to estimate needed for feeding, and thus, the influence of solvent on both reac- the Pt dispersion. Transmission electron microscopy (TEM) images tion and analysis is avoided. A well-known alkane isomerization were obtained on a Jeol 2010F field emission system operated at catalyst, Pt/HBeta, has been chosen as a bifunctional catalyst to 200 kV. A finely ground catalyst powder, pre-reduced at 300 °C test, with the acid sites of HBeta catalyzing the alkyl transfer reac- for 1 h, was dispersed ultrasonically in ethanol and then deposited tion [28] and Pt catalyzing the deoxygenation reaction. Anisole on a carbon coated copper grid for TEM measurement. The num- conversion over HBeta (acid zeolite function) and Pt/SiO2 (metal ber-weighted (dn) and the surface-weighted averageP particleP size 3 2 function) is included for comparison. (ds) were calculated using dn = Rnidi/Rni and ds ¼ nidi = nidi , respectively, where di is the particle size of ni. Approximately 200 particles from images of different places of each sample were 2. Experimental counted to calculate the dn and ds. The coke deposition was evalu- ated by temperature programmed oxidation of spent samples 2.1. Catalyst preparation and characterization using 5% O2/He with a Cirrus mass spectrometer (MS, MKS) detec- tor. The temperature was ramped from room temperature to The ammonium form of Beta zeolite (Zeolyst, CP814C, Si/ 900 °C with a heating rate of 10 °C/min. The quantification of car- 2 bon deposits was done by using calibrated pulses of CO2 and CO. Al = 19, SBET = 710 m /g) was calcined at 550 °C for 4 h to obtain HBeta. Pt/HBeta and Pt/SiO2 catalysts were prepared by incipient wetness impregnation of HBeta and SiO2 (HiSil 210, SBET = 2.2. Catalytic performance 2 135 m /g) with an aqueous solution of H2PtCl6Á6H2O (Aldrich) overnight and were then dried at 110 °C for 12 h, followed by Catalytic conversion of anisole was investigated in a fixed-bed calcination at 400 °C for 4 h. quartz tube (6 mm o.d.) reactor at atmospheric pressure. The X. Zhu et al. / Journal of Catalysis 281 (2011) 21–29 23 catalyst sample (40–60 mesh) was reduced in flowing H2 at 300 °C Table 1 for 1 h, and then the temperature was raised to 400 °C for reaction. Pt particle sizes estimated from XRD, TEM, and CO chemisorption.
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