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Article
Catalytic cracking of heavy aromatics and polycyclic
aromatic hydrocarbons (PAHs) over FCC catalysts.
Richard Pujro, Marisa Falco, and Ulises Sedran
Energy Fuels, Just Accepted Manuscript • Publication Date (Web): 19 Feb 2015
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Page 1 of 29 Energy & Fuels

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7 Catalytic cracking of heavy aromatics and
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11 polycyclic aromatic hydrocarbons (PAHs) over
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15 FCC catalysts
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20 Richard Pujro, Marisa Falco* and Ulises Sedran
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22 Instituto de Investigaciones en Catálisis y Petroquímica INCAPE (FIQ, UNL-CONICET)
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24 Santiago del Estero 2654, 3000 Santa Fe, Argentina.
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26 1
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ABSTRACT
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31 The distribution of products in the range of gasoline and middle distillates cuts obtained in
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33 the catalytic cracking of heavy aromatics and polycyclic aromatic hydrocarbons over a FCC
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35 catalyst was studied. 1-Phenyloctane, biphenyl, fluorene, 9,10-dihydrophenanthrene,
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37 naphthalene, phenanthrene, pyrene and benz[a]anthracene were used as model compounds of
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40 alkylaromatic, naphthenic-aromatic and polyaromatic hydrocarbons which are present in
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42 VGO and residual feedstocks in the FCC process. The catalyst was used in its fresh and
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44 equilibrium forms at 450 ºC in a CREC Riser Simulator reactor with reaction times from 2 to
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46 6 s. Thermal cracking reactions overwhelm the catalytic conversion of naphthenic-aromatic
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compounds such as fluorene and 9,10-dihydrophenanthrene. Under the same conditions, the
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51 fresh catalyst was more active than the equilibrium catalyst. The alkylaromatic, naphthenic-
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53 aromatic and polyaromatic hydrocarbons, showed catalytic conversions which increased,
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56 CORRESPONDING AUTOR
57 *Telephone: +54-342-4528062. Fax: +54-342-4531068. E-mail: mfalco@fiq.unl.edu.ar
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1
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3 were relatively stable and decreased, respectively, as a function of reaction time. The
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5 distribution of products suggested that most important reactions were thermal
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dehydrogenation, hydrogen transfer, ring opening, cracking and condensation. It was shown
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10 that all the model compounds are cracked, yielding particularly benzene in the gasoline range
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12 and coke.
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16 KEYWORDS: aromatics, PAH, LCO, gasoline, FCC
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21 1. INTRODUCTION
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23 Currently, the growing demand to process larger volumes of lower quality crude or resids and
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25 the need to optimize the quality of light cycle oil “LCO” and maximize yields of
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petrochemical raw materials are some of the most complex issues in the oil refining
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30 industry.1,2 As a consequence, changes are induced in the operation policies of the units of
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32 catalytic cracking of hydrocarbons (FCC), which is one of the most important conversion
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34 processes in present refineries.
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36 One of the drawbacks in the processing of residual or nonconventional hydrocarbon cuts
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39 which are added to typical vacuum gas oil (VGO) feedstocks, is the conversion of extremely
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41 large molecular structures,3 particularly, fully aromatic structures, which are also present in
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43 VGOs. This may adversely affect the quality of fuels; for example, making the content of
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45 aromatic hydrocarbons in LCO very large (typically between 50 and 70%),4 a fact which
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induces a very low cetane index of about 24-28. In general, these issues are dependent on the
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50 feedstock, the catalyst and the process conditions.
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52 However, the versatility of the FCC in processing different low quality, high molecular
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54 weight oil fractions opens to new chances of improving fuel quality and yield by means of
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56 new catalysts producing less aromatics.5,6 The particles of FCC catalysts include Y zeolite as
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1
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3 the main component supported on a matrix (active or inactive) together with various
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5 additives, fillers and binders. At present, the catalysts are custom made, according to the
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particular conditions in a refinery (feedstock, technology, production scheme).6,7
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10 Then, if specific catalysts are to be developed to decrease the selectivity to aromatic
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12 hydrocarbons in middle distillate cuts, it is necessary to know the mechanisms controlling the
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14 formation of these compounds in the cut, and the contribution to the group from the various
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16 components in the feedstocks. The formation of aromatics in the heavy gasoline-LCO boiling
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19 range could be evaluated through the conversion of model compounds, which are present at
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21 significant concentrations in the feedstocks or among products.8,9 However, so far, there exist
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23 few publications where the contribution from heavy polycyclic aromatic hydrocarbons in
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25 usual FCC feedstocks is investigated.10-12 On the contrary, more importance has been given to
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the study of the hydrogenation of polycyclic compounds,13-15 preferably naphthalene.16,17
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30 It is the objective of this work to study the conversion of alkylaromatic, naphthenic-
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32 aromatic and polyaromatic hydrocarbons which can be found in typical and residual cuts used
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34 as FCC feedstocks,18,19 with emphasis in the products belonging to the heavy end of gasoline
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36 and light end of LCO cuts, in order to generate useful information to assist in the formulation
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39 of new, more selective FCC catalysts. Eight different model reactants were used over the
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41 fresh and equilibrium forms of a commercial FCC catalyst in a CREC Riser Simulator
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43 laboratory reactor under very short contact times.
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2. EXPERIMENTAL SECTION
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50 2.1 Materials. Both the fresh (Cat-F) and equilibrium (Cat-E) forms of a commercial FCC
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52 catalyst which was formulated to maximize the LCO yield in the process were used. The
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54 main catalyst properties are summarized in Table 1.
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3 The total specific surface areas were calculated with the BET method, with 0.05<P/Pº<0.3,
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5 and the matrix areas were calculated with the t-plot method, with 3.5 Å<t<7.0 Å, using N2
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adsorption isotherms at 77 K, obtained with a Quantachrome Autosorb-1 equipment. The
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10 mesopore size distributions were calculated from the adsorption branch according to the BJH
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12 method20 and the zeolite content was determined from the micropore areas according to the
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14 Johnson’s method.21 The zeolite unit cell sizes (UCS) were determined with the ASTM D-
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16 3942-91 X-ray diffraction technique, using a Shimadzu XD-1 equipment. The contents of
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19 rare earths were determined by means of the inductively coupled plasma (ICP) method, using
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21 a Perkin Elmer Optical Emission Spectrometer OPTIMA 2100 DV.
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23 The nature, amount and strength of acidic sites of both catalysts were determined by
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25 means of the FTIR analysis of adsorbed pyridine (Merck, 99.5%) as a probe molecule in a
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Shimadzu FTIR Prestige-21 equipment. Pyridine adsorption was performed at room
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30 temperature and after successive desorptions at 150, 300 and 400 ºC, spectra were recorded at
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32 room temperature with a resolution of 4 cm-1 at pressure of 10-4 Torr. The amounts of
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34 Brönsted and Lewis acid sites were calculated from the integrated absorbance of the bands at
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36 1545 and 1450-1460 cm-1, respectively, by means of the integrated molar extinction
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39 coefficients, which are considered independent from the catalyst and site strength.22,23
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41 The model reactants used were 1-phenyloctane (C14H22, 98%, Aldrich), biphenyl (C12H10,
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43 >99%, SAFC), fluorene (C13H10, 98%, Aldrich), 9,10-dihydrophenanthrene (C14H12, 94%,
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45 Aldrich), naphthalene (C10H8, ≥99%, Merck), phenanthrene (C14H10, 97%, Fluka), pyrene
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(C16H10, >99%, Sigma) and benz[a]anthracene (C18H12, 99.5%, Supelco), their schematic
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50 representation being shown in Figure 1. Since most of the reactants are solid at room
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52 temperature, they were dissolved into benzene (99%, Cicarelli) in order to feed them easily to
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54 the reactor. Concentrations were 10 wt.% in all the cases, except for naphthalene (25 wt.%)
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56 and benz[a]anthracene (5 wt.%). The conversion experiments were performed in a CREC
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3 Riser Simulator reactor, which is a batch, fluidized bed laboratory reactor which closely
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5 mimics the conditions of the commercial FCC process.24 The unit has been described
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comprehensively elsewhere.25,26 Reaction times in the experiments were 2 and 6 s, reaction
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10 temperature was 450 ºC, which is used in units operating in the middle distillates mode,27 and
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12 mass catalyst to oil (solution) relationship was 1.12. The mass of catalyst was 0.15 g in all the
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14 cases. Experiments of purely thermal cracking (no catalyst in the reactor) were performed at
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16 the same temperature under the longest reaction time.
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19 2.2 Reaction and analysis equipments. The reaction products were analyzed by on-line
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21 standard capillary gas chromatography, using a 30 m long, 250 mm diameter and 0.25 mm
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23 film thickness, non-polar, dimethylpolysiloxane column. Product identification was
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25 performed with the help of standards and GC–MS analysis. The coke contents of the catalysts
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were assessed by means of a method with temperature-programmed oxidation and further
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30 methanation of the carbon oxides over a Ni catalyst, and quantified with the help of a FID
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32 detector.28 Mass balances (recoveries) closed to more than 95 % in all the cases.
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36 3. RESULTS AND DISCUSSION
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39 3.1. Reactivity of the solvent. The experiments of thermal cracking of the pure solvent
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41 benzene showed conversions to be only 0.02 %. This low conversion confirms the high
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43 thermal stability of benzene up to 1000 ºC.29
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45 When pure benzene was fed to the catalytic beds of Cat-F and Cat-E, the maximum
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conversions observed were 0.35 %, coke being by far the most important product. These
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50 results show that benzene is essentially inert to form gaseous products under these reaction
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52 conditions, thus being a proper choice as a vehicle to feed the model reactants to the reactor,
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54 assuming that its conversion products would not interfere with the catalytic systems under
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56 study.
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3 3.2. Thermal cracking. Figure 2 shows the results of thermal cracking (no catalyst in the
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5 reactor) of the various models compounds at 6 s reaction time, where some trends can be
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appreciated according to their different chemical structures. These results can be rationalized
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10 in the light of the knowledge of the pyrolysis of hydrocarbons, which typically includes
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12 reversible reactions of free radicals,30 the homolytic dissociation of covalent C-C or C-H
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14 bonds and the β-scission reaction.31
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16 The naphthenic-aromatic compounds (fluorene and 9,10-dihydrophenanthrene
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19 “9,10DHP”) are very reactive under thermal cracking reactions, with conversions which are
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21 as high as 86 % in the case of 9,10DHP. The reactivity of alkylaromatics compounds (1-
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23 phenyloctane “1PhO” and biphenyl) is intermediate, the highest conversion being 25%, case
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25 of 1PhO. The condensed polyaromatic compounds whose molecules include fused benzene
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rings are the least reactive among the model compounds, with thermal cracking conversions
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30 lower than 5 %. These results are consistent with observations from Al Darouich et al.(2006),
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32 who studied the thermal cracking of the (C6-C14) aromatic fraction of crude oil, including
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34 alkylaromatic and naphthenic-aromatic compounds, in the temperature range from 325 to
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36 500ºC, and reported that naphthenic-aromatic compounds were much less stable than
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39 alkylaromatic compounds.32 Maybe can check ref 32, to learn mechanism of bottoms cracking?

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41 Moreover, the difference in the thermal reactivities is particularly noticeable if similar
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43 structures such as those of 9,10DHP (H/C=0.86) and phenanthrene (H/C=0.71), which differ
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45 in the central ring being saturated or unsaturated, respectively, are compared. In effect,
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thermal conversions of 86% for 9,10DHP and 5% for phenanthrene were observed, thus
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50 confirming that the higher the unsaturation degree in a cyclic molecule, the higher its
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52 stability. This observation is also confirmed by the low thermal conversion shown by those
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54 molecules having fused aromatic rings (see Figure 2) and by the fact that as the number of
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more joined/fused aromatic rings, more stable (less reactive)
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1
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3 benzene rings in the molecule and its unsaturation degree increase, they become increasingly
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5 stable; for example, naphthalene converts to 4.55% and pyrene converts to 2.12%.
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The higher reactivity provided by the naphthenic character in the molecular structures
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10 studied, as confirmed by the observations described previously (e.g. cases of reactants such
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12 fluorene and 9,10DHP, refer to Figure 2), was also noticed by Moldoveanu,29 who suggested
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14 that cycloalkanes tend to form more stable compounds (highly unsaturated compounds) in the
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16 pyrolysis process. This behavior can be especially observed in the case of 9,10DHP (H/C=
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19 0.86) which transforms into its analogous unsaturated phenanthrene (H/C= 0.71), by scission
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21 of the C-H bond in carbon atoms 9 and 10, with a selectivity of 99%. When fluorene, with a
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23 saturated ring of five C atoms, is the reactant, benzene was observed with selectivity of 92%
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25 (Figure 3), suggesting that the breaking the C-C bond is favored.
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In the case of alkylaromatics 1PhO and biphenyl, the latter is more stable, showing a
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30 thermal conversion of 5%. Perez and Raimondo also observed that a molecule which has
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32 some structural similarity to that of biphenyl, such as 1-phenylnaphthalene, converted to only
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34 1.5% when pyrolyzed at 450 ºC.33 On the other hand, the high selectivity to benzene observed
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36 with these model compounds can be justified based on the dealkylation of the aliphatic side
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39 chain in 1PhO and the phenyl group in biphenyl (Figure 3), this case leading obviously to a
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41 higher yield of benzene in producing two phenyl groups per reacted molecule. In the case of
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43 1PhO minor yields of toluene, ethylbenzene, xylenes and C2-C8 olefins and paraffins besides
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45 benzene were also observed, which can be explained based on the scission of the C8 side
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chain. In that sense, Moldoveanu had reported that the formation of free radicals in the
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50 pyrolysis of alkylated aromatic hydrocarbons initiates with the scission of the bond between
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52 two carbon atoms with sp3 hybridation, particularly in the carbon atoms in the aliphatic side
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54 chain.29 Moreover, Burklé-Vitzthum et al. mentioned that alkyl aromatics with long side
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56 chains show the weakest bond located at the beta position in the side chain, close to the ring;
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3 thus, cracking products such as toluene and polyalkylbenzene of short chains would be
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5 favored.34
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The condensed polyaromatic model compounds naphthalene, phenanthrene and pyrene
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10 also showed important selectivities to benzene, though smaller than those of the other
11
12 reactants, given their higher thermal stability and minor H/C (refer to Figure 3).
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14 In summary, benzene is the main product in the thermal cracking of these model
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16 compounds, with the only exception of 9,10DHP, which shows phenanthrene as the most
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19 important product.
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21 3.3. Catalytic cracking. The conversions of the various model compounds over catalysts
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23 Cat-F and Cat-E are shown in Figure 4. In all the cases the conversions are higher on catalyst
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25 Cat-F than on catalyst Cat-E; this is expected, given the lower amount of crystalline material
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27
and acidic sites in the last catalyst, after being equilibrated in a commercial FCC unit.
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30 According to the values of thermal conversion shown in Figure 2, this process should be
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32 considered as part of the process of catalytic cracking and for some of the model reactants
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34 plays an important role, which is even more important at the low catalytic conversions
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36 observed on catalyst Cat-E.
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39 Particularly, it can be considered that the overall catalytic cracking of naphthenic-aromatic there are some
compounds that can
40 be cracked easily
41 compounds (fluorene and 9,10DHP) over both catalysts is essentially governed by the through thermal
42 cracking alone
43 thermal cracking process. In the case of alkylaromatic compounds (1PhO and biphenyl) the
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45 contribution from the thermal reactions when they are converted on both catalysts Cat-F and
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Cat-E is expected to be considerable. A much lower contribution from thermal cracking to
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50 the overall conversion process is expected in the cases of the condensed polyaromatic
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52 compounds, particularly with molecules which include three o more unsaturated rings, where
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54 the catalytic effect can be noticed more significantly (Figures 2 and 4).
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3 The reactivity observed in the case of 1PhO (linear C8 alkyl aromatic) (Figure 4) confirms
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5 the observations by Corma et al. in the cracking of long side chain alkyl aromatics over Y
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zeolite.35 The eight carbon atoms side chain is long enough to be subjected to the whole set of
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10 catalytic cracking reactions of hydrocarbons, as shown by the products which are described
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12 later.
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14 Moreover, if biphenyl, fluorene and 9,10DHP, which are naphthenic-aromatic compounds,
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16 are considered similar structures with different number of carbon atoms (Figure 1), their
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19 conversions increased with the increasing number of carbon atoms in the molecules. The
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21 increasing conversions may be related to the naphthenic-aromatic structure which makes
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23 easier the scission of the C―C and C―H bonds.36 Appleby et al. also observed this behavior
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25 in studying the production of coke in catalytic cracking of naphthenic-aromatic and
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27 Can check ref 11 to
polyaromatic compounds over a fresh silica-alumina catalyst at 500ºC,11 where the see mechanism of
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coke formation
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30 conversion of naphthenic-aromatic compounds were biphenyl (6.3%), fluorene (13.2%) and
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32 9,10DHP (20.3%).
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34 It was also observed in the case of the condensed polyaromatic hydrocarbons that This is unlike the case
35 for thermal cracking
36 conversion increased as long as the number of unsaturated ring increased (Figure 4),
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39 becoming close to those of the naphthenic-aromatic compounds, as a consequence of the these polyaromatic is
cracked to
40 napthenic-aromatic?
41 production of coke. This is consistent with observations from Appleby et al. naphthalene Because it is turning to
42 coke?
43 (7.7%), phenanthrene (16%) and pyrene (15.8%).11 On the contrary, Dupain et al. in the
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45 cracking of an paraffinic gas oil spiked with model reactants such as naphthalene, anthracene
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and phenanthrene, observed an increase of their concentrations, particularly of naphthalene,
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50 thus concluding that cracking reactions in aromatic feedstocks are limited to alkylbenzenes or
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52 the paraffinic fraction.12 These different behaviors observed if the condensed polyaromatic Need to read ref 12 on
how is the result is
53 different from this
54 hydrocarbons are fed pure (this work and Appleby et al.11) or taking part of a complex paper
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56 mixture such as gas oil (Dupain et al.12) can be explained if it is considered that they do not
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3 compete for acidic sites with other hydrocarbons. Pujro et al. found that the isolated fractions
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5 (saturated, aromatic and resin) of ATR resids convert extensively when reacted under FCC
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conditions over commercial equilibrium catalysts at 550 ºC.37 However, the differences in the
8
9
10 yields of the main hydrocarbon groups from the various fractions are noteworthy and reveal
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12 their nature; moreover, it is not possible to assess the yields of given groups from the
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14 conversion of the resid by the direct addition of the yields from the different fractions, due to
15
16 interactions among the various fractions and the corresponding products.
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19 It can be seen in Figure 4 that longer reaction times impact differently on the various
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21 model reactants. In effect, the increase in conversion as a function of reaction time was very
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23 important in the case of 1PhO (about 15 percentage points over Cat-F and 7 percentage points
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25 over Cat-E), and moderate in the cases of biphenyl, fluorene and 9,10DHP (less than five
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27
percentage points for both catalysts). In the case of condensed polyaromatic hydrocarbons,
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30 naphthalene showed a moderate increase, while phenanthrene, pyrene and BaA, showed a
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32 decrease in their conversions after increasing the reaction time, which was very significant in
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34 the case of pyrene and BaA. This different behavior for condensed polyaromatic compounds,
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36 as compared with alkylaromatic and naphthenic-aromatic compounds, can be assigned to Feed that has many
37 compound that can
38 easily turned to coke
39 their higher yield of coke, which induces catalyst deactivation. Condensed polyaromatic can deactivate
40 catalyst
41 compounds are considered strong coke precursors or that they may strongly adsorb on acidic
42
43 catalysts. It was reported in studies about coke oxidation on Y zeolite with pyrene as the
44
45 model compound,38 that the amount of pyrene adsorbed corresponded to approximately one
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47
molecule per supercage, that TPO experiments showing that more than 90 % of the adsorbed
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50 pyrene molecules was recovered as CO and CO2, demonstrating that this type of molecule
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52 can be strongly adsorbed on the zeolite surface.
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54 3.4. Reaction products. The occurrence of unsaturated rings in the molecules of the
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56 model compounds suggests that the set of reactions would initiate through the electrophilic
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3 attack of acidic protons in the catalyst surface. This was also proposed in the cracking of
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5 alkylated benzenes such as isobutyl benzene,39 of molecules such as tetralin and
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7
naphthalene,40 and in the formation of coke from benzene,41 since the benzene rings are a rich
8
9
10 source of electrons (nucleophile)36 and its resonating character favors the formation of a
11
12 positive, also resonating, species which is known as a benzylic carbocation, with a stability
13
14 similar to that of a secondary carbocation.42
15
16 A heterogeneous group of products with one to fourteen carbon atoms per molecule,
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19 including C1-C2 light gases, C3-C6 olefins, C4-C8 paraffins, C6-C8 naphthenics, benzene,
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21 toluene, xylenes, indane, dimethylindane, and smaller amounts of decalin, tetralin,
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23 naphthalene, biphenyl, methyl naphthalene and phenanthrene is the consequence of the
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25 conversion of 1PhO (Bz-C8). A set of reactions is to be expected; for example, dealkylation
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27
reactions which can be complemented by the cracking, disproportionation and cyclization
28
29
30 reactions of C8 olefinic chains.43 In effect, the side chain can be protonated and suffer
31
32 scission at different locations and even cyclization to produce tetralin, followed by hydrogen
33
34 transfer reactions that lead to naphthalene. These reactions and their corresponding products
35
36 are consistent with the observations by Watson et al. (1997) about the reaction pathways in
37
38
39 the catalytic cracking of alkylbenzenes (including phenyloctane) over REY at 500 ºC.44 These
40
41 authors propose that the reactions initiate via protonation of the aromatic ring or paraffin
42
43 adsorption of the alkyl side chain, forming a five-centered carbonium ion and giving place to
44
45 dealkylation by beta-scission. Moreover, Corma et al. identified three main routes in the
46
47
cracking of alkylaromatics with long side chains over USY zeolite at 500 ºC: dealkylation of
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49
50 the benzene ring to yield benzene and an olefin; protolytic cleavage of the alkyl side chain to
51
52 yield an olefin and an alkyl benzene or a paraffin and an alkenyl benzene, and alkylation of
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54 an intermediate alkylaromatic with short chain olefins, followed by ring closing.35,45
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3 Minor productions (<0.5 wt.%) of light gases, toluene, xylenes and naphthalene were
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5 observed in the cracking reaction of biphenyl, together with the most important products
6
7
benzene and coke (Table 2), thus suggesting that the dealkylation of phenyl groups, promoted
8
9
10 by the formation of a benzylic carbocation,39 is the most important reaction. Coke could be
11
12 the consequence of oligomerization and condensation reactions.
13
14 Among the products from the catalytic cracking of fluorene, a naphthenic-aromatic
15
16 compound, low yields (<0.5 wt.%) of light gases, C7-C10 alkylbenzenes, tetralin, indane,
17
18
19 biphenyl and naphthalene were observed, together with significant yields of a phenanthrene
20
21 isomer (C14H10), benzene and coke, suggesting that it undergoes the ring opening reaction in
22
23 its five member saturated ring and further cracking of the biphenyl-type bridge (Ph―Ph),
24
25 following a reaction scheme similar to that of biphenyl. In the catalytic cracking of fluorene
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27
over silica –alumina at 500 ºC, Appleby et al. observed a yield of 1.3 wt.% of H2,11
28
29
30 suggesting that the molecule dehydrogenates either through the thermal hemolytic scission of
31
32 the C-H bond on carbon number 9 or through the hydrogen transfer reaction on the acidic
33
34 sites of the catalyst.
35
36 However, in the case of 9,10DHP, the experimental conditions in this work promote its
37
38
39 thermal cracking reactions, making phenanthrene to be the most important product in its
40
41 catalytic conversion, given the dehydrogenation of the saturated ring. Even so, minor yields
42
43 (<1 wt.%) of light gases, benzene, toluene, ethylbenzene, biphenyl and C2-C5 olefins and
44
45 paraffins were observed, suggesting that the saturated ring can be opened and the biphenyl-
46
47
type bridge can be further cracked on the catalyst acidic sites. Experiments of
48
49
50 hydroconversion of phenanthrene over bifunctional metal-acid catalysts showed
mechanism of
51 cracking
13
52 hydroaromatics compounds among the products, including 9,10DHP, suggesting that it phenanthrene (BP =
53 644 F)
54 could suffer the opening of its saturated six member ring following a purely acidic
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3 mechanism, to be initiated with the formation of either a benzilic or secondary carbocation by
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5 the attack of the surface protons to the external aromatic rings.
6
7
In condensed polyaromatic molecules, the action of the zeolite protons would favor the
8
9
10 stability of the unsaturated rings located at the extreme positions, as shown in reactions of
check the zeolite
11
36 proton reaction with
12 electrophilic substitution of polyaromatics compounds, a fact also observed in the catalytic unsaturated
13 polyaromatics
14 cracking of naphthalene on FCC catalysts.40 In relation to this, Korre and Klein studied the compounds
15
16 hydrogenation of heavy oil, evaluating the impact of the structure of fully aromatic
17
18
19 compounds with one to four aromatic rings and confirmed that central aromatic rings are
20
21 preferentially saturated against extreme rings.14 Intermediate compounds with partially
22
23 saturated rings are susceptible to ring opening and further cracking of the biphenyl-type
24
25 bridge (Ph―Ph), similarly to 9,10DHP, thus explaining the occurrence of light gases,
26
27
benzene, toluene, xylenes, naphthalene and coke from phenanthrene, pyrene and BaA.
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29
30 Particular products can be identified from the conversion of each model compound; for
31
32 example, fluorene and phenanthrene from pyrene; and biphenyl, phenanthrene and pyrene
33
34 from BaA.
35
36 The hydrogen needed for the saturation of whichever aromatic ring in the hydrogen
37
38
39 transfer reactions could be provided by the dehydrogenation reaction in the thermal cracking
40
41 steps or by the formation of coke from the own model reactants. For example, Appleby et al.
42
43 reported a yield of gases of 1.2 wt.% (76% hydrogen) in the catalytic cracking of
44
45 phenanthrene, and a yield of gases of 1.9 wt.% (84% hydrogen) in the catalytic cracking of
46
47
pyrene.11
48
49
50 In summary, it was shown that all the model reactants can be cracked by this acidic
51
52 catalysts, demonstrating that both thermal (homolytic C-C and C-H scissions) and catalytic
53
54 (hydrogen transfer, cracking, dealkylation, ciclyzation, oligomerization) reactions occur
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56 simultaneously, giving place to high benzene and coke yields (Table 2), and much lower
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3 yields of light gases and liquids (<1 wt.%). Conversions increased with the number of carbon
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5 atoms per molecule and, as expected, they were higher on the fresh catalyst (Figure 4).
6
7
If the thermal and catalytic selectivities of benzene in the experiments with alkylaromatic
8
9
10 reactants, 1PhO and biphenyl are compared (Figure 3 and Table 2), it can be seen that they
11
12 were lower in the experiments with both catalysts. This fact can be explained in the light of
13
14 the catalysts promoting reactions other than dealkylation (which was the only one in the
15
16 thermal experiments); also the formation of coke on the catalysts has to be considered (Table
17
18
19 2), which could certainly consume part of the benzene molecules.
20
21 In the case of the naphthenic-aromatic compounds it was observed that, for the case of
22
23 fluorene, the selectivity to benzene does not change when the catalyst is present, even though
24
25 other reactions and coke formation occur, where benzene can take part. On the contrary, the
26
27
catalysts favor the production of benzene from 9,10DHP, thus confirming that the catalysts
28
29
30 promote the ring opening reactions.
31
32 The selectivity to benzene in the catalytic conversion of condensed polyaromatic
33
34 molecules shows that it is possible to crack these highly condensed hydrocarbon molecules
35
36 on these acidic catalysts at FCC conditions.
37
38
39 In general, longer reaction times produced a decrease in benzene yields, together with an
40
41 increase in coke yields (see Table 2), strongly suggesting that benzene is involved in the
42
43 production of coke. In the cases of phenanthrene, pyrene and BaA, the yield of coke could
44
45 not be considered exclusively based on the consumption of benzene and other reaction
46
47
products, but also on the own reactants, given their strongly aromatic character, which makes
48
49
50 them coke precursors. This fact is reflected on the decrease in the conversions of these model
51
52 reactants as a function of time (see Figure 4). Moreover, it can be seen in Table 2 and Figure
53
54 4 that the yields of coke increase as the number of carbon atom per molecule increases, as
55
56 also observed by Appleby et al.11 and Corma et al.46
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5 4. CONCLUSION
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Various model compounds (alkylaromatics, naphthenic-aromatics and condensed
8
9
10 polyaromatic hydrocarbons), which are usually present in residual or VGO feedstocks to the
11
12 FCC process, showed differences in both their thermal and catalytic conversions on FCC
13
14 catalysts. The thermal cracking of naphthenic-aromatics compounds at 450 ºC was the
15
16 highest among the model compounds used, less important for alkylaromatics and very low for
17
18
19 the condensed polyaromatics. Particularly for fluorene and 9,10DHP (naphthenic-aromatic
20
21 compounds) the thermal cracking reactions govern the total conversion process.
22
23 The catalytic conversions were the highest over the fresh catalyst Cat-F, which has higher
24
25 content of zeolite and acidity. The distributions of products showed that most important
26
27
reactions were the thermal cracking when no catalyst was present and hydrogen transfer, ring
28
29
30 opening, cracking and condensation when catalysts were used, which are initiated by the
31
32 electrophilic attack of protons on the surface of the Y zeolite.
33
34 It was shown that all the model compounds are cracked, yielding particularly benzene in
35
36 the gasoline range and coke.
37
38
39 These conclusions could support the formulation of FCC catalysts aimed at selectively
40
41 cracking given types of hydrocarbons, according to the compositions of the feedstocks.
42
43
44
45 ACKNOWLEDGEMENTS
46
47
This work was performed with the financial assistance of National University of Litoral
48
49
50 (UNL), Secretary of Science and Technology (Santa Fe, Argentina) (CAID 2011 #501
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52 201101 00329 LI); CONICET (PIP 1257/09) and the National Agency for Scientific and
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54 Technological Promotion (PICT 2010/2123).
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3 REFERENCES
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12 (41) Gates, B.C.; Katzer, J.R.; Schuit G.C.A. Chemistry of catalytic processes; McGraw-Hill:
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14 USA; 1979, pp 1-111.
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16 (42) McMurry, J. Química Orgánica, 7ma Ed; Cengage Learning Editores S.A. de C.V.:
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21 (43) Smirniotis, P.G.; Ruckenstein, E. Ind. Eng. Chem. Res. 1994, 33, 800-813.
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23 (44) Watson, B. A.; Klein, M. T.; Harding, R. H. Appl. Catal. A 1997, 160, 13-39.
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25 (45) Corma, A.; Miguel, P.J.; Orchillés, A.V.; Koermer, G. J. Catal. 1994, 145, 181-186.
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(46) Corma, A.; Miguel, P.; Orchillés, A. J. Catal. 1994, 145, 171-180.
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5 TABLES
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12 Table 1. Properties of the catalysts used.
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14
15
16 Specific Average
17 Metals Acidity
Zeolite RE surface area mesopore
18 (Ni+V) (µmol Py g-1)
19 Catalyst (m2g-1) diameter
20 Brönsted Lewis
UCS load Si/Al content content Matrix Total
21 (1545 cm-1) (1450-1460 cm-1)
22 (nm) (wt.%) (wt.%) (wt.%) nm 150ºC 300ºC 400ºC 150ºC 300ºC 400ºC
23
24 Cat-F 2.456 22.00 3.5 0.94 0.000 92 243 8.45 128.5 102.1 76.3 118.1 42.4 36.9
25
Cat-E 2.430 9.83 14.2 0.70 0.095 102 162 8.92 5.0 5.1 5.0 13.6 11.0 10.9
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10 Table 2. Selectivities of benzene and coke (%) in the catalytic cracking of the model
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12 compounds.
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16
17 Cat-F Cat-E
18
benzene coke benzene coke
19
20 Reaction time (s) 2 6 2 6 2 6 2 6
21
22 1PhO 51.94 36.46 21.59 26.33 74.64 63.29 9.59 14.04
23 Biphenyl 64.93 55.75 32.56 42.21 82.02 67.43 14.66 28.59
24
25 Fluorene 78.75 79.52 7.24 11.53 89.48 87.27 2.50 4.61
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27
9,10DHP 12.27 14.38 9.45 15.10 14.77 11.69 2.00 4.08
28 Naphthalene 60.68 51.02 35.11 41.29 87.86 83.43 8.58 14.53
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30 Phenanthrene 66.37 49.75 25.14 44.65 76.11 60.10 15.91 32.01
31 Pyrene 96.74 93.50 2.62 5.66 92.55 75.32 5.73 20.93
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33 BaA 80.04 67.76 16.87 29.18 89.35 80.49 8.05 17.51
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13 1-Phenyloctane Biphenyl Fluorene 9,10-Dihydrophenanthrene
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15
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19 Naphthalene Phenanthrene Pyrene Benz[a]anthracene
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21
22 Figure 1.
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Figure 2.
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100
10
11 90
12 80
13
70
14
15 60
16 50
17
40
18
19 30
20 20
21
10
22
23 0
24 1PhO Biphenyl Fluorene 9,10DHP Naphthalene Phenanthrene Pyrene
25 Model Reactants
26
27
28
Figure 3.
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100
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90
11 Cat-F
12 80
13 70
14 60
15 50
16 40
17
30
Conversion (wt.%)

18
20
19
20 10
21 0
22 90
23 80
Cat-E
24 70
25
60
26
50
27
28 40
29 30
30 20
31 10
32 0
33 1PhO Biphenyl Fluorene 9,10DHP Naphthalene Phenanthrene Pyrene BaA
34
Model Reactants
35
36
37 Figure 4.
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10 Figure 1. Schematic representation of the model reactants.
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16 Figure 2. Thermal conversion of model reactants.
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19 Fillings: (□) alkylaromatics, (░ ) naphthenic-aromatics, (|||) condensed polyaromatics.
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21
22
23
24
25
26 Figure 3. Selectivity to benzene in the thermal conversion of the model reactants. Fillings as
27
28 in Figure 2.
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33
34
Figure 4. Conversion of the model reactants over catalysts Cat-F and Cat-E.
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37 Reaction times 2 s (white) and 6 s (gray). Fillings as in Figure 2.
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6 1-Phenyloctane Biphenyl Fluorene 9,10-Dihydrophenanthrene
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14 Naphthalene Phenanthrene Pyrene Benz[a]anthracene
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1 90
2
80
Conversion (wt.%)
3
4 70
5 60
6
7 50
8 40
9
10 30
11 20
12
13 10
14 0
15 1PhO Biphenyl Fluorene 9,10DHP Naphthalene Phenanthrene Pyrene
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Benzene selectivity (%)
3 80
4 70
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7 50
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10 30
11 20
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90
1
80
Cat-F
2
3 70
4 60
5
6 50
7 40
8
9 30
Conversion (wt.%)

10 20
11
12 10
13 0
14
15 90
16 80
Cat-E
17
18 70
19 60
20
50
21
22 40
23
30
24
25 20
26 10
27
28 0
29 1PhO Biphenyl Fluorene 9,10DHP Naphthalene Phenanthrene Pyrene BaA
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