TITLE OF PRESENTATION (14 pt, Arial, bold, centered)：演講題目（14號字體宋體加粗居中）

1、.SUPPORT INFLUENCE ON Ni-based CATALYSTS FOR HYDRODEOXYGENATION REACTION OF BIOFUEL-PRECURSORSS. Echeandia, V.L. Barrio, J.F. Cambra, P.L. Arias1, S.A. Khromova21School of Engineering (UPV/EHU), c/ Alameda Urquijo s/n, 48013 Bilbao (Spain) 2Boreskov Institute of Catalysis, Pr. Akad. Lavrentieva, 5,

2、Novosibirsk, RussiaIntroduction Biomass is a renewable alternative to fossil raw materials for the production of liquid fuels and chemicals. Pyrolized biomass liquid fractions contain oxygenated molecules that must be removed to improve the stability of these liquid fuel precursors. A hydrotreating

3、process, hydrodeoxygenation (HDO), is commonly used for this purpose 1. Therefore study of their deoxygenation is a subject of interest. Phenol HDO is generally accepted to proceed via two parallel reaction pathways 2: O-C bond cleavage giving aromatic products (direct hydrogenolysis), or aromatic r

4、ing hydrogenation before O-C bond cleavage (combined hydrogenation-hydrogenolysis). In the latter route, alicyclic products are formed and the corresponding alicyclic alcohols appear as short-lived intermediates 3. The influence of catalyst formulations and activations on those two HDO mechanisms wi

5、ll be fully discussed. The phenol, as a model compound, is used in order to screen different hydrotreating catalysts in HDO. The supports studied are: Al2O3, CeO2, ZrO2, ZrO2-CeO2.Experimental Activity tests were carried out in a bench-scale fixed-bed catalytic reactor with 0.2 g of catalysts. Hydro

6、gen and liquid feed were fed to the reactor in a molar ratio of 100:1 in H2 : phenol. The experimental conditions were as follows: temperature in the range 423573 K, total pressure of 1.5 MPa and space velocity of 0.5 gphenol/gcatalyst·h corresponding to a model feed consisting of 1 wt% phenol

7、and n-octane as solvent. The liquid products were analyzed by off-line MSD for identification and FID for quantification. Results and discussionSteady-state conversion data for phenol HDO over reduced Ni-based catalysts are represented in Figure 1. These data are the average of conversion archived d

8、uring 6 h of time on-stream. During this time the phenol conversion changes were < 3 %. As it can be seen in the Figure 2, in which phenol conversion is represented, nearly total phenol conversion was reached and none or little deactivation seems to have been occurred, except in the case of the a

9、lumina-supported catalysts that present a drop of approximately 6%. Cat1 Cat2 Cat3 Cat4Cat1 Cat2 Cat3 Cat4Figure 1. Influence of temperature on phenol conversion with Ni-based catalysts.Figure 2. Influence of temperature on products selectivity with Ni-based catalysts.For the catalysts studied the p

10、roducts with the highest selectivity was cyclohexanol at low temperatures and cyclohexane at high temperatures (Figure 2). The most important products were cyclohexanol, cyclohexane and benzene. This fact indicates a unique reaction pathway in the HDO of the phenol, which is the hydrogenation-hydrog

11、enolysis. First hydrogenation took place converting phenol into cyclohexanol, especially at low temperatures. Then, hydrogenolysis occurred through the breakage of the oxygen-carbon bond and finally a subsequent hydrogenation converted the cyclohexanol into cyclohexane. It is noteworthy that at high

12、 temperature (573 K) and a WHSV of 0.5 h-1, in the catalysts supported with ceria showed the direct hydrogenolysis contribution started and benzene as product appeared. Also at the highest temperature methylcyclopentane was also formed from cyclohexane isomerization. ConclusionsThe main conclusions

13、of this research are: i) Ni-based catalysts are very promising in biomass derived liquids HDO; ii) for the Ni-based catalysts the phenol conversion is very high and it seems that the preference route of reactions is the hydrogenation-hydrogenolysis; iii) with these catalytic systems alicyclic produc

14、ts are formed and the corresponding alicyclic alcohols appear as short-lived intermediates specially at low temperatures; iv) the stability in these catalysts seems to be quiet high although a small deactivation was found where Al2O3 was used as support. References1 E. Furimsky, Appl. Catal., A 199 (2000), 147-190.2 Viljava, T.R., Doctoral Thesis, Helsinki University of Technology, Espoo, Finland, 2001.3 I. Gandarias, V.L. Barrio,