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Ind. Eng. Chem. Res. 2008, 47, 54025412

Skeletal Isomerization of Butene in Fixed Beds. 1. Experimental Investigation and Structure-Performance Effects
Matias Kangas, Narendra Kumar, Elina Harlin, Tapio Salmi, and Dmitry Yu. Murzin*,
Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, bo Akademi UniVersity, FI-20500 Turku/bo, Finland, and Neste Oil, P.O. Box 310, FI-06101 PorVoo, Finland

An experimental investigation of structure-performance effects in zeolite catalyzed skeletal isomerization has been carried out. Two structurally different, medium-pore-size zeolites (H-TON and H-FER) with similar acidities were compared in butene skeletal isomerization. While both catalysts proved to be efcient in the test reaction, their deactivation behavior differed substantially. H-FER exhibited signicantly higher initial isobutene yields and selectivities, and the catalyst performance was also more stable with time-on-stream. H-TON, on the other hand, needed prolonged operation times in order to achieve product distributions comparable to those of H-FER. The predominant route to isobutene was found to be the monomolecular one, with the bimolecular paths of butene largely responsible for byproduct formation. H-TON was more selective toward disproportionation and, owing to its slightly larger pore dimensions, hydrogen transfer products. H-TON was also observed to be less sensitive to feed reactant than H-FER was, conrming previous theoretically calculated structure effects. Coke belonging to both aliphatic and aromatic families was detected over both zeolites, although the coke formed on H-FER was overall heavier and more aromatic in nature. The tested zeolites could be regenerated by burning of the carbonaceous deposits in air, and both catalysts regained almost all of their initial activities.
1. Introduction Most of the oil rening processes in operation today involve the use of solid acid catalysts, and the vast majority of these catalysts belong to the zeolite family. The major zeolitecatalyzed processes found in todays reneries include uid catalytic cracking (FCC), hydrocracking, hydroisomerization, and dewaxing of distillates and lubrication oils.1 Since their introduction some 40 years ago, the application of zeolites have helped to increase many renery process efciencies through improved product yields and selectivities, while at the same time meeting ever-increasing demands on product quality. Opportunities for further commercialization of zeolite-based processes can be found, for instance, in the transformation of light olens, by oligomerization into fuels and lubes, or by isomerizing linear C4 and C5 olens into their branched, and more valuable, counterparts. The production of renery-decient isobutene by skeletal isomerization of linear butenes has received a lot of attention in the past decade. The reaction has gathered industrial interest because of an increasing demand for isobutene in the production of methyl tert-butl ether (MTBE), a fuel additive that improves the properties of gasoline. Although the use of MTBE as an octane booster is decreasing, the demand for isobutene is still high as the isobutene feedstocks formerly used in the production of MTBE are nding new uses as raw materials in alternative octane-enhancing components for gasoline.2 The academic discussion of skeletal isomerization has mainly centered on the reaction mechanism315 and the benecial effect of coking on reaction selectivity.35,8,13,1520 Zeolites with channel-type structure and pore diameters between 4 and 5.5 have been shown to be suitable materials for catalyzing the skeletal isomerization of n-butene into
* To whom all correspondence should be addressed. Fax: 358 2 215 4479. E-mail: dmurzin@abo.. bo Akademi University. Neste Oil.

isobutene.7 This range of pore diameters is found in 10membered ring (10 MR), also known as medium-pore-size, zeolites. Among the medium-pore zeolites, ZSM-22 (TON)21 and ferrierite (FER)22 have both been shown to be selective and stable in skeletal-isomerization applications. The scope of the present work is to experimentally compare the activities of two proton form zeolites with TON and FER structures and to study their deactivation behavior with timeon-stream (TOS). The study also aims at collecting data for kinetic modeling of skeletal isomerization and any relevant side reactions. 2. Experimental Section 2.1. Synthesis and Characterization of Catalysts. K-ZSM22 zeolite was synthesized from two solutions, according to the method described by Byggningsbacka et al.23 The rst solution was prepared by diluting the silica source, Ludox AS-40, in distilled water, and the second solution was obtained by dissolving the aluminum source, Al2(SO4)2 18 H2O (Merck), in distilled water. The organic template 1,6-diaminohexane (Fluka) and KOH (Merck) were added to the aluminumcontaining solution. The solutions were subsequently stirred for 15 min, after which the solutions were combined under conditions of vigorous stirring. Mixing the two solutions at ambient temperature resulted in the formation of a white gel, which was stirred for an additional 30 min. The actual synthesis of K-ZSM-22 was carried out in a Teon-lined autoclave at 433 K for 72 h. The synthesized material was ltered, washed with distilled water, and dried at 383 K for 12 h, after which the organic template was removed by calcination of the sample at 823 K for 15 h. The ammonium form of the zeolite was obtained by ion-exchange of K-ZSM-22 with 1 M NH4Cl (Merck) solution. The ion-exchanged zeolite was then washed free of chloride ions and dried for 12 h at 323 K, and a nal

10.1021/ie800061q CCC: $40.75 2008 American Chemical Society Published on Web 06/25/2008

Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008 5403

calcination of the sample at 823 K for 10 h was carried out in a mufe oven to obtain the proton form H-ZSM-22 (H-TON) zeolite. NH4-FER was obtained from Zeolyst International (CP 914) and was transformed into proton form (H-FER) by a step calcination procedure in a mufe oven. The structure and phase purity of the tested zeolites were determined by an X-ray diffractometer (Phillips PW 1820), and crystal shape and size was studied using scanning electron microscopy (Cambridge Leica 360). The bulk silicon-to-aluminum ratio was determined by X-ray uorescence (Siemens SRS 303), and the specic surface areas were measured by the nitrogen adsorption method (Sorptometer 1900, Carlo Erba Instruments). The catalysts were outgassed at 473 K prior to the measurements, and the Dubinin method was used to calculate the specic surface area. The acidity of the investigated catalysts was measured by infrared spectroscopy (ATI Mattson FTIR) using pyridine (>99.5%, a.r.) as a probe molecule. Samples of the zeolites were pressed into thin self-supporting wafers (8 mm) of approximately 10 mg. Pyridine was adsorbed at 373 K for 30 min and then desorbed by evacuation at different temperatures (523, 623, and 723 K) to obtain the distribution of acid site strengths. The spectra were recorded at 373 K using a spectral resolution equal to 2 cm-1. Spectral bands at 1545 and 1450 cm-1, respectively, were used to identify Brnsted (BAS) and Lewis acid sites (LAS). Quantitative results were calculated from the integrated absorbance areas of the corresponding peaks using the integrated molar extinction coefcients of Emeis.24 The acidity was also measured by temperature-programmed desorption of NH3 (NH3-TPD). The sample was adsorbed with ammonia at 473 K and later ushed with helium at the same temperature. A heating rate of 20 K/min was used. 2.2. Isomerization Experiments. A xed-bed minireactor operating in the vicinity of atmospheric pressure connected to a gas chromatograph (GC), equipped with an online gas-phase autosampler, was used in the study. The reactor was packed with roughly 0.5 g of catalyst particles (pelletized, crushed, and sieved to 100-125 m), and the bed was kept in place with quartz wool and sand. These, together with a packing of glass beads in front of the catalyst bed, provided a uniform ow of gases to the bed and preheated the reactants. The reactor was placed in an oven, and feedback for heating control was provided by a thermocouple inside the catalyst bed. The efuent from the reactor was passed through a heated line to the gas chromatograph (Agilent Technologies 6890N), equipped with a ame-ionization detector and a capillary column (HP-PLOT Al2O3 50 m 530 m 15 m). The GC column was able to separate all components up to, and including, pentenes. The heavier compounds could not be sufciently separated and were grouped according to carbon number into hexenes, heptenes, and octenes when calculating the results. The grouping limits were determined by injecting a mixture of n-parafns and assuming that the straigh-chain alkane is the rst peak to appear for each group. The catalysts were activated in situ for 2 h at 773 K in air followed by drying for 2 h at 723 K in a nitrogen atmosphere. When the catalyst bed had reached reaction temperature, the reactant and nitrogen were introduced and the rst sample was taken after 10 min on stream. The experiments were carried out with reactant partial pressures varying from 0.1 to 1.0 atm, temperatures ranging from 523 to 673 K, and weight hourly space velocities (WHSVs) between 6 and 88 h-1. Regeneration of the used zeolite catalysts was done by in situ burning of the deposited coke. After completed reaction,

the reactant ow was switched to synthetic air and the temperature was raised from the reaction temperature to 773 K with a heating rate of 1 K/min. The catalyst was kept at 773 K for 4 h and was then dried in nitrogen atmosphere at 723 K for an additional 1 h before the reactor was ramped down by 10 K/min to reaction temperature. 2.3. Coke Characterization. The nature of the coke formed on the catalysts used in this work was studied by dissolution of the zeolite structures and extraction of the soluble part of the coke. The structures of the coked zeolites were destroyed by treatment in 2 mL of 40% hydrouoric acid (Merck) for every 0.25 mg of used catalyst. Following dissolution of the zeolite structure, approximately 10 mL of dichloromethane (J.T. Baker) was added to recover the soluble part of the coke. After ltration and separation of the phases, analysis of the organic phase with GC-MS (Agilent Technologies 5973N) was made. Quantitative measurements of the carbon content were obtained by oxidation of the carbonaceous deposits in either Stro hlein CS-5000 or Leco CHN 2000 elemental analyzers. 2.4. Cracking Experiments. By adding an evaporator to the experimental setup, the cracking behaviors of the linear 1-octene and the heavily branched diisobutene isomers were also studied. The cracking experiments were performed at a temperature of 623 K with an octene-to-nitrogen molar ratio of approximately 1-5 and WHSV varying between 2.4 and 40 h-1. 3. Results and Discussion 3.1. Catalyst Structures and Characterization. Ferrierite (FER) is a two-dimensional zeolite containing two perpendicularly intersecting channel systems.25 One channel consists of 10-membered rings (10 MR) with dimensions of 4.2 5.4 , and the other consists of eight-membered rings (8 MR) with dimensions 3.5 4.8 . The TON structure is unidimensional and has 10 MR pores with dimensions of 4.6 5.7 .25 The morphology of the two zeolites was studied with scanning electron microscopy (SEM), and akelike crystals were observed for FER, whereas the crystals of TON were shaped like needles, typical of 1-D crystal structures. The typical crystal sizes approximated from SEM micrographs were 1 1 0.1 m for FER and 1 0.1 0.1 m for TON. Graphical representations of the two structures are shown in Figure 1. The gure depicts the 10 MR pores of the frameworks viewed along [001]. Isobutene has been placed inside the micropore space of the zeolites, and parts of the host structures and the guest molecule are represented by 70% of their CPK volumes, illustrating the limited space available to the reactants and products. The results of the characterizations are summarized in Table 1. Surprisingly, the Brnsted acidities measured by Py-FTIR for the two zeolites were very similar (180 vs 178 mol/g), although their bulk Al contents differ quite a lot. However, the choice of pyridine as a probe molecule for ferrierite type materials has been challenged.2628 The theory of severely diffusion-controlled transport of pyridine into the zeolite pores was, therefore, tested by increasing the adsorption temperature and time. Performing the adsorption at 473 K and prolonging the adsorption time from 0.5 to 20 h revealed an additional 80 mol/g (30%) of medium-strength Brnsted sites in H-FER, while the amount of BAS stayed mostly unchanged for H-TON. Both catalysts saw a dramatic increase in the amount of LAS found when saturated at elevated temperatures. The overall Lewis acidity was increased by 50% for H-TON and almost 200% for H-FER, suggesting that most of the extra framework Al is located in the 8 MR pores of H-FER.

5404 Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008

Figure 1. Graphical representation of isobutene in the 10 MR channels of FER and TON: (a) FER and (b) TON.

The amount of acid sites measured by NH3-TPD for the two tested catalysts were also very close (590 and 560 mol/g, for FER and TON, respectively), although the quantitative results by NH3-TPD differed signicantly from the ones obtained by Py-FTIR. The majority of the ammonia desorbed between 573 and 773 K, for both catalysts, and they both exhibited a NH3 desorption maximum at 723 K, indicating that the samples have similar distribution acid site strengths. The FER zeolite used (Zeolyst CP 914) has also been studied using other acidity measurement techniques, such as temperature-programmed desorption-thermogravimetric analysis (TPD-TGA) with n-propylamine,29,30 and total Brnsted acid site concentrations between 350 and 530 mol/g have been obtained, indicating that the use of Emeis extinction

coefcients for FER results in too low concentrations. A comparison between reported extinction coefcients in a recent publication31 also suggests that the coefcients are not portable from one material to another or from one IR technique to another. Another explanation is that NH3 and the linear propylamine diffuse much faster inside the zeolite crystals than pyridine and that they can access sites unavailable to pyridine. 3.2. Isomerization of n-Butene. Although 1-butene is the reactant initially introduced into the reactor, n-butene (i.e., 1-butene, cis-2-butene, and trans-2-butene) can be considered the reactant because double-bond migration in 1-butene is signicantly faster than skeletal isomerization or any other

Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008 5405
Table 1. Characterization of the Zeolites Used H-FER FTIR of Adsorbed Pyridine (mol/g) BAS LAS weaka 10.3 3.6 mediumb 60.5 2.1 c strong 108.7 2.2 sum 179.4 8.0 X-ray Fluorescence Si/Al 30 Nitrogen Physisorption specic surface area, (m2/g) 432 micropore volume, (mL/g) 0.141 H-TON BAS 11.4 74.7 91.4 177.6 40 295 0.085 LAS 10.7 6.1 2.7 19.5

a Desorbing between 523 and 623 K. b Desorbing between 623 and 723 K. c Remaining after desorption at 723 K.

chemical reaction involving 1-butene. A constant equilibrium among the linear butene isomers gives the following denitions: Conversion )
(1-butene)in - (n-butene)out (1-butene)in (product)out (1-butene)in

Figure 2. n-Pentene-isopentene equilibrium, H-TON and H-FER: 2, 573 K; O, 623 K; 9, 673 K; WHSV ) 6-44 h-1; pHC ) 0.1-1.0 atm.

100%

(1) (2)

Yield ) Selectivity )

100% 100%

(product)out (1-butene)in - (n-butene)out

(3)

3.2.1. Isobutene Formation. Three main reaction mechanisms for skeletal isomerization of linear butenes into isobutene have been proposed in the literature; the monomolecular,4,7,8,12,13,15 the pseudomonomolecular,3,5 and the bimolecular6,911,14 reaction routes. The monomolecular route involves only one n-butene molecule and converts it exclusively into isobutene, and 100% selectivity is, thus, theoretically possible. The bimolecular mechanism proposals can be further subdivided into two separate routes; the classical bimolecular6,14 and the codimerization911 paths. In the classical bimolecular proposal, n-butene dimerizes into dimethylhexene that undergoes further isomerization and nally cracks into one isobutene and one n-butene. In the codimerization scheme, one linear and one branched butene combine to form a trimethylpentene, which cracks into two isobutene molecules. The codimerization route, also known as the autocatalytic route, is potentially the more selective of the two bimolecular pathways. Guisnet et al.5 and Andy et al.3 suggested a pseudomonomolecular mechanism, somewhat similar to the codimerization route, in order to explain the apparent change in mechanism with increasing time-onstream observed in many studies. The sites for this, supposedly very active and selective, route are docked carbenium ions located inside the zeolite pores. The mechanism avoids the thermodynamically unstable primary product carbenium ion, which is usually associated with monomolecular branching via opening of the protonated cyclopropane transition state. Nevertheless, the pseudomonomolecular reaction mechanism has been heavily criticized.8,12,32,33 Skeletal isomerization of pentene is much easier to catalyze than branching of butene,6,12 and there is a general consensus that branching of molecules with ve or more carbons occur monomolecularly. As shown in Figure 2, equilibrium among the pentene isomers was always reached for the experimental conditions employed in this work. It is, moreover, improbable that the pseudomonomolecular reaction or bimolecular codimerization mechanisms would operate only for skeletal isomerization of butene but not for pentene. Both routes involve carbenium ions as active sites and, thus, avoid formation of unstable primary carbenium ion-like reaction intermediates or transition states but proceed instead through energetically more

Figure 3. Rates of n-butene conversion (9) and isobutene formation () as a function of reactant relative partial pressure (pn-butene/ptot); closed symbols, TOS ) 10 min; open symbols, TOS ) 46 h; H-FER, T ) 623 K; WHSV ) 12 h-1; ptot ) 1.0 atm.

favorable secondary carbenium ions only. In line with previous studies,6,12 n-pentene was in this study isomerized much faster than n-butene, precluding the pseudomonomolecular and codimerization routes as the predominant ones for both tested zeolites. If the main route to isobutene is the classical bimolecular one, an increase in reactant partial pressure should result in signicantly higher rates of isobutene formation. The possible pressure effect on product yield and selectivity was, therefore, studied over H-FER. The initial rate of n-butene conversion and isobutene formation versus butene relative partial pressure is illustrated in Figure 3. Although an increase in conversion with increasing n-butene partial pressure is observed, the apparent rate of isobutene formation over nondeactivated H-FER is actually decreasing. The simultaneous increase in conversion and byproduct selectivity indicates that skeletal isomerization is less sensitive to reactant partial pressure than byproduct formation via oligomerization-cracking reactions and/or that formed isobutene readily transforms into byproducts in consecutive bimolecular reactions. At high n-butene partial pressures, probably both monomolecular and bimolecular mechanisms are operating. The amount of isobutene formed monomolecularly over fresh FER has been estimated to 70%34 and that over fresh TON has been estimated to between 80 and 90%.8,35 In agreement with the ndings of Domokos et al.,4 the initial rate of isomerization in this work is almost constant (zero order in butene) for highly diluted feeds, and as the 1-butene partial

5406 Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008

Figure 4. Relative isobutene yield, WHSV ) 12 h-1, pHC ) 0.5 atm: (a) H-FER; (b) H-TON; square, 673 K; circle, 623 K; upward-facing triangle, 573 K; left-facing triangle, 523 K.

Figure 5. Evolution of isobutene yield: (a) T ) 573 K, (b) T ) 673 K. open circle, H-TON, WHSV ) 44 h-1; open square, H-TON, WHSV ) 6 h-1; solid circle, H-FER, WHSV ) 44 h-1; solid square, H-FER, WHSV ) 6 h-1. pHC ) 0.5 atm.

pressure approaches zero (the dashed lines in Figure 3 are extrapolated lines), the overall rate of butene conversion and isobutene formation meet. The initial rate of 4 g/(gcat h) corresponds to 71 mmol/(gcat h), which is close to previously reported values of 644 and 686 mmol/(gcat h) for FER and similar experimental conditions. As the catalyst deactivates, the overall conversion decreases, causing an increase in the apparent rate of isobutene formation and selectivity, especially in cases where the thermodynamic equilibrium between butene isomers is established. However, the apparent rate of isobutene formation with a 1:9 dilution is continuously decreasing with time-onstream with hardly any increase in selectivity. This is a strong indication that carbonaceous deposits are not necessary for highly selective operation over the tested H-FER catalyst and might even have an adverse effect on isobutene yield. The relative isobutene yield, dened as the yield at time t divided by the initial yield measured at TOS ) 10 min, for the experiments carried out with a WHSV value of 12 h-1, is shown in Figure 4. The gure illustrates the differences in time-onstream behavior with regard to isobutene yield for the two tested zeolites. With the exception of the runs performed at 523 K, the absolute yields of isobutene for both catalysts continuously increase during the initial stages of reaction and reach approximately 35 mol % after 25 h TOS. It is clear that H-FER is the more stable of the two zeolites and that H-TON needs longer operation times to achieve high isobutene selectivities. At 673 K, the isobutene yield over H-TON more than doubles, from 17 to 36 mol %, during the rst 25 h, while the initial

yield over H-FER for the same conditions is already close to 30 mol %. The apparent activation energy for H-FER seems to be signicantly lower than that for H-TON, as the initial yield at 523 K for H-FER is already 16 mol %, whereas only 4 mol % isobutene is observed over H-TON. Both zeolites exhibit decreasing trends in isobutene yields with TOS at the lowest temperature. A direct comparison of isobutene yield at 573 and 673 K is shown in Figure 5. The initial yield of isobutene is again always higher for H-FER than for H-TON. The yield of the desired product at 573 K also stays higher for H-FER throughout the experiments, whereas H-TON exhibits higher isobutene yields at longer times on stream at 673 K. The different deactivation behavior is also, once more, evident from Figure 5. A small but rapid increase during the rst hours, followed by an almost linear change in isobutene yield, is typical for H-FER, whereas the change in yield with time-on-stream is even more for H-TON. The differences in deactivation behavior can be attributed to the presence of 8 MR channels in FER (causing the initial rapid change) and the differences in crystal morphologies between the two zeolites. The needlelike crystals of TON have larger relative contribution of external (nonselective) sites than the akelike crystal structure of FER, which could be the reason that prolonged reaction times are needed for highly selective operation of H-TON. 3.2.2. Olenic Byproduct Formation. Beside the desired isobutene, large amounts of unsaturated byproduct are also formed. The unwanted reactions yielding olenic byproduct

Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008 5407
Scheme 1. Proposed Reaction Scheme: MH ) Methylheptene, DMH ) Dimethylhexene, and TMP ) Trimethylpentene

Table 2. Product Distribution (in mol %) for H-FER, WHSV ) 6 h-1, pHC ) 0.5 atm temperature TOS
LHCa ethene propane propene isobutane n-butane n-butene isobutene pentenes hexenes heptenes octenes
a

573 K 10 min
0.1 0.5 1.0 11.0 1.3 2.2 27.2 28.7 13.7 4.8 6.5 3.1

623 K 46 h
0.0 0.0 0.1 5.4 0.4 0.6 40.4 37.8 6.2 1.7 3.6 3.9

673 K 46 h
0.0 0.3 0.2 13.7 0.7 0.5 32.5 29.9 13.8 3.0 3.7 1.8

10 min
0.1 2.2 2.1 18.3 2.0 2.4 23.2 21.7 16.4 5.6 5.0 1.0

10 min
0.3 4.1 2.7 21.1 1.7 2.2 24.4 20.7 13.5 5.6 2.9 0.9

46 h
0.0 0.5 0.1 13.8 0.6 0.5 36.2 30.3 12.3 2.1 2.3 1.2

LHC ) methane + ethane.

Table 3. Product Distribution (in mol %) for H-TON, WHSV ) 6 h-1, pHC ) 0.5 atm temperature TOS
LHC ethene propane propene isobutane n-butane n-butene isobutene pentenes hexenes heptenes octenes
a
a

573 K 10 min
0.1 0.6 1.6 12.9 1.3 3.9 22.7 23.5 16.0 6.0 8.0 3.5

623 K 46 h
0.0 0.1 0.4 5.5 0.4 3.6 40.0 32.9 5.2 1.0 4.6 6.2

673 K 46 h
0.0 0.4 0.9 10.6 0.4 3.9 33.4 32.4 9.5 1.8 4.4 2.3

10 min
0.2 2.9 4.6 19.7 2.2 5.0 17.0 16.1 16.9 7.5 6.4 1.6

10 min
0.5 6.8 6.7 25.1 1.9 5.5 16.5 13.6 12.2 6.0 4.2 0.9

46 h
0.0 1.1 0.8 12.1 0.3 3.5 37.3 32.0 8.1 1.5 2.5 0.7

LHC ) methane + ethane.

include disproportionation of butene into propene and pentene and various dimerization and oligomerization reactions. The side-reactions taking place in butene skeletal isomerization over H-FER were studied by Kangas et al.,36 and the proposed reaction network is reproduced in Scheme 1. Byproduct formation was the most pronounced in the experiments with long residence times and elevated reaction temperatures. The product distributions for the experiments carried out with a WHSV value of 6 h-1 are given in Tables 2 and 3. The main behavior with regard to product distribution and time-on-stream trends was roughly the same for both catalysts, with increases in butene and octene yields with TOS, while the rest of the components in the system exhibited decreasing tendencies in yields with prolonged operation time. For fresh catalysts, H-FER has 5-8 mol % higher yields of both the reactant and product butenes, translating into superior initial selectivites compared to those of H-TON. However, the

isobutene selectivities for H-TON increase signicantly with time-on-stream, and in the experiments carried out at 623 and 673 K, H-TON exhibits higher isobutene selectivites and yields than H-FER after 46 h. The dramatic increases in isobutene yields and selectivites coincide with similar decreases for disproportionation products. Propene and pentene were always the most abundant byproducts, in some cases accounting for more than one-third of the total yield. The yield of pentene versus the yield of propene for the n-butene experiments over H-TON is illustrated in Figure 6a. The bending of the curve for 673 K can be seen as an indication of one or more additional paths for the formation of propene at higher reaction temperatures. H-FER exhibited similar trends with the exception that the pentene yields at 623 and 673 K presented maxima,36 which implies that pentene cracks into propene and ethene and that this reaction has a much faster rate of deactivation than other routes yielding propene. Figure 7 further illustrates the differences in pentene and propene yield for the two catalysts at the highest reaction temperature of 673 K. The pentene-to-propene ratios for fresh catalysts are approximately the same for both zeolites, but while it stays rather constant for H-TON, the ratio is initially increasing for H-FER and approaches a constant value, slightly higher than that for H-TON, as the catalyst deactivates. The maximum amounts of ethene obtained in this work were 4 mol % for H-FER and 7 mol % for H-TON, suggesting that pentene cracking occurs also on H-TON but that the deactivation behavior of the reaction does not noticeably deviate from the other reactions taking place over H-TON. Cracking of pentene involves a primary carbenium ion-like intermediate and might, thus, be more difcult to catalyze than the rest of the reactions represented in Scheme 1. However, monodimensional 10 MR zeotypes and zeolites, including proton-form FER, have been found to catalyze pentene cracking via monomolecular -scission,37 and propene and ethene have been observed as primary products over FER when introducing 1-pentene as a reactant under similar reaction conditions.6 The yields of hexene (Figure 6b) and heptene (Figure 6c), which are dimers of propene and codimers of propene and butene, respectively, are both typically around 1-7 mol % each, although they behave quite differently with regard to propene. The plots of hexene versus propene yields exhibit a clear bending at higher conversions, which suggests an additional reaction involving propene and hexene. Heptene, on the other hand, displays nearly linear dependencies with regard to propene, especially at 673 K. This indicates that heptene is rapidly formed from propene and butene, with a reaction order of close to zero with regard to butene. For H-FER, the linear relationship between heptene and propene, shown in Figure 8, is even clearer. The yield of octene as a function of propene is shown in Figure 6d, and it behaves differently compared to the other pseudocomponents. The fact that the curves go through a maximum shows that octene and propene are involved in consecutive reactions with at least part of the propene formed from octene. For modeling purposes, which will be discussed in detail in an accompanying paper, the main reaction routes need to be identied. The reaction network was checked by estimating the fraction of hexene produced via cracking of surface-bound nonene. Scheme 1 shows that hexene can be formed either from dimerization of propene or from cracking of an adsorbed C9 species. As propene takes part in most of the reactions yielding byproduct, the C3)to-C5) ratio is a good test of the reaction network. If pentene and propene were primarily produced by cracking of octene, the molar ratio between them would be around 1. As evident from Figures

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Figure 6. Major byproduct distribution, H-TON; 2, 573 K; O, 623 K; 9, 673 K; T ) 573-673 K, WHSV ) 6-44 h-1, pHC ) 0.5 atm.

Figure 8. Heptene yield versus propene yield, H-FER; 2, 573 K; O, 623 K; 9, 673 K; WHSV ) 6-44 h-1; pHC ) 0.5 atm. Figure 7. Pentene yield versus propene yield for H-FER (2) and H-TON (9): T ) 673 K, WHSV ) 6-44 h-1, pHC ) 0.5 atm.

6a and 7, the observed ratios can differ signicantly from this and the completeness of the reaction network can be assessed by checking under which conditions the sum of molecules originating from propene and pentene are equal. The sum of C3 and C5 molecules is dened in the following manner,
) ) ) ( ) ) C3 ) C) 3 + C3 - C2 - xC6 + 2 1 - x C6 + C7 ) ) C5 ) C) 5 + C2 + xC6

(4) (5)

where x denotes the fraction of hexene formed from nonene (Scheme 1). The fraction of hexene produced from nonene as

a function of temperature and time-on-stream is shown in Figure 9. For weight hourly space velocities g 44 h-1, the fraction always exceeds 1, which means that cracking of hexene is faster than dimerization of propene and that part of the formed hexene further cracks into two propene molecules. For H-FER, the fraction is very close to 1 and almost independent of temperature or TOS, suggesting that no changes in predominant routes to byproduct occur with elevated temperature or prolonged operation time. For H-TON, the fraction is steadily increasing with time-on-stream and it exhibits an obvious dependence on reaction temperature, with larger portions of the hexene formed from nonene at lower temperatures. For lower weight hourly space velocities (not shown), and consequently longer residence

Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008 5409

Figure 9. Fraction of hexene produced through nonene cracking: (a) H-FER and (b) H-TON; 2, 573 K; O, 623 K; 9, 673 K; WHSV ) 44 h-1; pHC ) 0.5 atm.

Figure 10. Olen-to-parafn ratios, T ) 673 K, WHSV ) 6 h-1, pHC ) 0.5 atm: (a) H-FER and (b) H-TON; 9, C3; O, n-C4; 2, iso-C4.

times, the fraction of hexene produced from nonene cracking decreases for both zeolites. 3.2.3. Hydrogen Transfer Reactions. In solid acid catalyzed reactions of hydrocarbons, deactivation occurs mainly through formation of coke that covers the active sites and/or blocks the zeolite channels. The creation of coke is usually considered to involve many consecutive steps; oligomerization of smaller olens to form larger ones, cyclization, transformation into monoaromatics through bimolecular hydride transfer, alkylation of the formed monoaromatic, and further ring closure of the alkyl-substituted monoaromatic into a bicyclic compound that in turn undergoes further hydrogen transfer reactions to nally produce a biaromatic molecule. The formed biaromatic coke can then be further transformed into triaromatics, etc. Accompanying the formation of each aromatic ring are three bimolecular hydrogen transfer reactions, in which propene and butene act as hydrogen acceptors and transform into their saturated counterparts. Hydrogen transfer involves a net transfer of H2 from one molecule to another, producing hydrogenated and dehydrogenated products. The reaction consists of protonation, hydride transfer, and deprotonation elemementary steps.38 Hydride transfer of branched molecules is faster than those involving linear isomers and has been shown to be very sensitive to pore size and structure in skeletal isomerization,7 aromatization,39 and cracking reactions.40,41 Hydride transfer is generally thought of as the rate-limiting step in hydrogen transfer, and the bimolecular elementary step exhibits sterical constraints in many zeolites. The hydride abstraction step has been reported to be sterically more hindered

than olen addition,42 and the correlation between parafns and olens is, therefore, also a convenient way to evaluate pontential shape-selectivity effects. Examples of the olen-to-parafn ratios for the C3 and C4 molecules in H-FER and H-TON are shown in Figure 10. Although TON has larger pores than FER, hydride transfer to isobutene seems more restricted in H-TON than in H-FER. While H-FER exhibits the expected order of the ratios if no severe spatial restrictions are present, the ratio between isobutene and isobutane for H-TON is considerably higher than anticipated with values approximately 1 order of magnitude larger than those of nonbranched hydrocarbons. This indicates that the transition states in bimolecular hydride transfer involving isobutene are signicantly more constrained in the channels in TON than in FER. At the intersection between the 8 MR and 10 MR pores in FER, spherical cavities of 6-7 are formed,16 and this seems sufciently large to accommodate at least some of the transition states needed for hydrogen transfer to isobutene. Self-hydrogenation of isobutene in these cavities is still spatially restricted as the transformation from isobutene to isobutane over FER has been reported to be 84 and more than 206 times slower than the corresponding n-butene to n-butane reaction. A somewhat more accurate estimation of sterical constraints in butene isomerization is the ratio of isobutane to n-butane (i/n). If the self-hydrogenation is controlled thermodynamically, the ratio should be around 0.8 for the conditions used in this work.16 If the hydrogen transfer reactions are kinetically controlled, and n-butene and isobutene are present in sufcient amounts, the ratio should be above the thermodynamic value, due to the much faster reaction of branched molecules. Houz -

5410 Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008
Table 4. Isobutane-to-n-Butane Ratios, WHSV ) 6 h-1, pHC ) 0.5 atm H-FER 10 min 673 K 623 K 573 K 0.75 0.81 0.58 46 h 1.36 1.34 0.63 H-TON 10 min 0.35 0.43 0.33 46 h 0.08 0.11 0.10

vic ka and co-workers7 studied shape selectivity in skeletal isomerization of butene over a wide range of zeolites and discovered that the ratio was clearly below the thermodynamic value for small-pore (8 MR) catalysts, while hydrogen transfer to isobutene was a lot faster than that to n-butene for largepore (12 MR) zeolites, giving ratios well-above 0.8. Mediumpore (10 MR) molecular sieves were found to be the most selective and stable for 1-butene skeletal isomerization, and the ratio of branched to linear butane varied around the thermodynamic one. The values for TON and FER zeolites were approximately the same as those obtained in this study (Table 4). For fresh zeolites, the i/n ratio obtained in this work for H-FER is approximately twice as high as that for H-TON, although the total amount of hydrogen transfer products for H-TON is 2-fold that of H-FER. Surprisingly, the isobutaneto-n-butane ratio increases with time-on-stream for H-FER, although the relative concentration of isobutene among the butene isomers is decreasing. If the main effect of coking is increasing the steric constraints for reaction and diffusion, a narrowing of the micropores by coke deposits should slow down hydrogen transfer to isobutene more than to n-butene,16 thus decreasing the i/n ratio. This peculiarity can be explained by different deactivation rates of the acid sites in 10 MR and 8 MR pores in FER. It has been proposed that the 8 MR channels deactivate faster than 10 MR ones;17,43 since 8 MR pore structures have been shown to be far more selective toward n-butane than isobutane,7 and as long as a signicant part of the n-butane is formed in the 8 MR channels, an increase in the i/n ratio with TOS seems logical. The ratios of isobutane to n-butane for H-FER exhibited maxima after 10-20 h TOS in all the experiments. For H-TON, the ratio was always decreasing. 3.2.4. Deactivation and Regeneration. Deactivation by coking always accompanies butene skeletal isomerization, at least for conditions close to those employed industrially. For most 10 MR zeolites, coking has proven benecial, in the sense that it usually results in higher isobutene selectivities. The exact role of the carbonaceous deposits and their mode of formation and location are still subjects of discussion.35,8,13,1517,19,20,32,35 The chemical nature of the coke formed in this study was investigated by dissolution of the zeolite structure, extraction with dichloromethane, and analysis by GC-MS. No clear trends in the nature of the carbonaceous deposits as a function of temperature were observed, although higher butene partial pressures resulted in more aromatic and less aliphatic coke. Overall, the coke formed on H-FER was heavier and more aromatic in nature compared to that formed on H-TON. The distribution of coke components was estimated by approximating the area of the chromatographic peaks to the amount of corresponding compounds. The aliphatic coke family, mainly consisting of long linear olens, made up roughly 50% of the deposits on H-TON and between 20 and 40% of those on H-FER. For H-TON, the aromatic compounds were distributed equally among species containing one, two, or three aromatic rings, whereas components with two and four aromatic rings seemed to be favored in H-FER. The amounts of lighter species, such as toluene and xylenes, are probably underestimated, since they possess high volatilities and parts of them most likely

evaporate with the dichloromethane. Toluene and xylenes have also been observed directly by GC in the reactor efuent (see Scheme 1).44 The most abundant coke species on both H-TON and H-FER were alkyl-substituted naphthalenes. Quantitative measurements of the coke content were obtained by temperature-programmed oxidation, and for H-FER, the amount of carbon after approximately 50-70 h time-on-stream varied between 6 and 9 wt %, which is in agreement with previous reports for FER catalysts.3,4,14,43 The amount of deposits on H-TON was roughly one-half that of H-FER, ranging from 3 to 4.5 wt %. Coke content increased with increasing temperature for both catalysts. High-temperature coke was also less soluble in dichloromethane than deposits formed at lower temperatures. The tested zeolites could be regenerated by burning the carbonaceous deposits in synthetic air, and both catalysts regained almost all of their initial activity. The results of repeated reactions with fresh and one, three, and ve times regenerated zeolites are depicted in Figure 11. After ve regenerations, both zeolites have lost roughly 5 mol % in conversion and isobutene yield, although the loss in activity per regeneration is decreasing. 3.3. Cracking of Octene Isomers. There exists 15 structural isomers of octene, and the isomers chosen in the present study represent the two extremes. 1-Octene has a fully linear skeleton and lacks any side -chains, whereas diisobutene contains three methyl groups, including a geminal pair. As such, they behave differently when cracked and when diffusing through the narrow zeolite channels of the medium-pore zeolites. A summary of the experimental ndings is presented in Table 5, together with the results from 1-butene isomerization under comparable conditions. Overall, H-FER is more sensitive to reactant octene isomer as far as product distribution is concerned and always exhibited higher yields of isobutene. As expected, the closest to desired product distribution was obtained when feeding diisobutene. Cracking of 1-octene produced the least amounts of isobutene, and feeding 1-butene yielded a distribution of products in between the two. The sum of C3-C4 hydride transfer products for H-TON is, for all tested reactants, approximately 2-fold that of H-FER. H-TON is also more selective toward disproportionation. When cracking 1-octene, the olen product distribution (Table 5) was almost the same for H-FER and H-TON, and the reaction produced mostly propene and pentene. Although isobutene cannot be formed as a primary product from n-octene cracking, equilibrium between the skeletal isomers of butene was observed for H-FER. The deactivation was the most severe for 1-octene cracking with a decrease in conversion for both zeolites in excess of 10 mol % during the rst hour of reaction. In the same time frame, losses in activity of approximately 2-3 mol % were observed when either diisobutene or 1-butene were fed as reactants. Diisobutene cracking is usually considered the most facile of the octene isomer -scission reactions and is theoretically 100% selective to isobutene. Still, the disproportionation products account for one-third of the yield when cracking diisobutene over fresh H-TON. This indicates that geminally branched isomers experience severe mass transfer problems in the zeolite pores or that formed isobutene rapidly undergoes further transformations producing mostly propene and pentene. There is an ongoing discussion in the scientic literature on the shape-selective effects,45 steric constraints,18,46 and diffusional resistance47 of mono- and dibranched hydrocarbons in TON. Because of the steric constraints of the branched molecule in the tested catalysts, the cracking reaction of diisobutene might also predominantly take place on the outer surface of the zeolite crystals.

Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008 5411

Figure 11. Repeated reactions with fresh (solid symbols) and 1-5 times regenerated (open symbols) catalysts; 2, isobutene yield; , conversion. T ) 623 K, WHSV ) 44 h-1, pHC ) 0.5 atm: (a) H-FER and (b) H-TON. Table 5. Comparison of Main Product Distributions over the Fresh Zeolites for the Cracking and Isomerization Experiments, T ) 623 K reactant catalyst
n-butene isobutene C3) + C5) C3-C4 alkanes conversion n-C4)/iso-C4) (C3) + C5))/C4) IE

diisobutenea H-FER
26 36 22 2 96 0.73 0.35 1.66

1-octeneb H-TON
22 27 32 4 98 0.80 0.64 0.87
b

1-butenec H-TON H-FER

23 22 35 7 77 1.07 0.77 0.63
c

H-FER
19 18 46 1 96 1.06 1.26 0.39

H-TON
17 16 37 12 83 1.06 1.11 0.44

Yields (mol %) 17 15 41 3 88 1.18 1.28 0.36

a TOS ) 15 min, pC8 ) 0.25 atm, WHSV ) 7.5 h-1. WHSV ) 6.0 h-1.

TOS ) 15 min, pC8 ) 0.15 atm, WHSV ) 7.5 h-1.

TOS ) 10 min, pC4 ) 0.50 atm,

The isomerization efciency, dened as IE ) iso-C4)/(C3) + C5 ), for the two zeolites and all the reactants is compared in Table 5. For 1-octene cracking and 1-butene isomerization, the IE value of H-FER is only slightly higher than that for H-TON, but for the case of diisobutene cracking, the efciency of H-FER is close to double that of H-TON. The isomerization efciency also more than doubled during the rst hour on stream, for both tested zeolites, when introducing diisobutene into the reactor. At the same time, the conversion mostly stayed unchanged, which supports the theory of consecutive reactions of isobutene forming propene and pentene. Although both tested catalysts deactivated the most when 1-octene was fed as reactant, no changes in isomerization efciencies were observed in this case. Taken together, the cracking experiments support the conclusions of Domokos et al.48 Using applied molecular simulations over FERand TON-type zeolites in siliceous forms, they found that the docking energies for C8 isomers that can potentially be cracked into isobutene were more favorable for FER, whereas potentially nonselective C8 isomers were equally stabilized in the two structures.
)

4. Conclusions Both the H-TON and H-FER zeolites used in this study have proven to be efcient catalysts in n-butene skeletal isomerization. Although the acidities and pore dimensions of the two zeolites were similar, their catalytic behavior differed drastically. H-FER exhibited signicantly higher initial isobutene selectivities compared to H-TON, and it was also the more stable with time-on-stream of the two catalysts. For the conditions used in this study, isobutene was formed mainly via the monomolecular route, while the bimolecular paths of butene were largely responsible for byproduct formation. The predominant route to byproduct was dispropor-

tionation, yielding propene and pentene. Of the two zeolites used in this study, H-TON was more selective toward disproportionation. The observed product distribution of H-TON was also less sensitive to feed reactant than that of H-FER, conrming previous theoretically calculated structure effects. The steric constraints in the two zeolite structures were assessed from the ratio of parafns to olens and the ratio of isobutane to n-butane. Because of the slightly larger pore dimensions of H-TON, it was more selective toward hydrogen transfer products, with total parafn yields approximately twice that of H-FER. FER, on the other hand, has channel intersections large enough to accommodate some of the transition states yielding isobutane, and the hydrogen transfer reaction of isobutene was, therefore, 1 order of magnitude faster in H-FER than in H-TON. From the ratios of isobutane to n-butane, and pentene to propene, the different deactivation rates of the 8 and 10 MR channels in H-FER could also be observed. Both zeolites experienced deactivation through coking during the experiments, with roughly 10-30% losses in n-butene conversion after 2 days time-on-stream. Coke belonging to both aliphatic and aromatic families was detected. Overall, the coke formed on H-FER was heavier and more aromatic in nature. The tested zeolites were easily regenerated by burning of the carbonaceous deposits in synthetic air, and both catalysts regained almost all of their initial activity.

Acknowledgment This work is part of the activities at bo Akademi Process Chemistry Centre within the Finnish Centre of Excellence Program (2000-2011) by the Academy of Finland. Financial support from Graduate School in Chemical Engineering for M.K. is gratefully acknowledged.

5412 Ind. Eng. Chem. Res., Vol. 47, No. 15, 2008

Literature Cited
(1) Degnan, T. F. Applications of zeolites in petroleum rening. Top. Catal. 2000, 13 (4), 349. (2) Aittamaa, J.; Jakkula, J.; Lindqvist, P.; Koskinen, M.; Linnekoski, J.; Krause, O.; Sourander, M.; Ignatius, J.; Pyha lahti, A. Process for producing a fuel component. U. S. Patent US6613108, 2003, assigned to Fortum Oil and Gas. (3) Andy, P.; Gnep, N. S.; Benazzi, E.; Travers, C. Skeletal Isomerization of n-Butenes: II. Composition, Mode of Formation, and Inuence of Coke Deposits on the Reaction Mechanism. J. Catal. 1998, 173, 322. (4) Domokos, L.; Lefferts, L.; Seshan, K.; Lercher, J. A. Isomerization of Linear Butenes to Isobutene over Medium Pore Zeolites: I. Kinetic Aspects of the Reaction over H-FER. J. Catal. 2001, 197, 68. (5) Guisnet, M.; Andy, P.; Gnep, N. S.; Travers, C.; Benazzi, E. Origin of the positive effect of coke deposits on the skeletal isomerization of n-butenes over a H-FER zeolite. J. Chem. Soc., Chem. Commun. 1995, 16, 1685. (6) Guisnet, M.; Andy, P.; Gnep, N. S.; Benazzi, E.; Travers, C. Skeletal Isomerization of n-Butenes: I. Mechanism of n-Butene Transformation on a Nondeactivated H-Ferrierite Catalyst. J. Catal. 1996, 158, 551. (7) Houz vic ka, J.; Hansildaar, S.; Ponec, V. The Shape Selectivity in the Skeletal Isomerisation of n-Butene to Isobutene. J. Catal. 1997, 167, 273. (8) Houz vic ka, J.; Hansildaar, S.; Nienhuis, J. G.; Ponec, V. The role of deposits in butene isomerization. Appl. Catal., A 1999, 176, 83. (9) de Me norval, B.; Ayrault, P.; Gnep, N. S.; Guisnet, M. Shape Selectivity of HFER Zeolites as Responsible for the Positive Effect of Their Si/Al Ratio on the Selectivity to n-Butene Isomerization into Isobutene. Catal. Lett. 2004, 98 (4), 211. (10) de Me norval, B.; Ayrault, P.; Gnep, N. S.; Guisnet, M. Mechanism of n-butene skeletal isomerization over HFER zeolites: A new proposal. J. Catal. 2005, 230, 38. (11) de Me norval, B.; Ayrault, P.; Gnep, N. S.; Guisnet, M. n-Butene skeletal isomerization over HFER zeolites: Inuence of Si/Al ratio and of carbonaceous deposits. Appl. Catal., A 2006, 304, 1. (12) Me riaudeau, P.; Tuan, V. A.; Le, N. H.; Szabo, G. Selective Isomerization of n-Butene into Isobutene over Deactivated H-Ferrierite Catalyst: Further Investigations. J. Catal. 1997, 169, 397. (13) Me riaudeau, P.; Naccache, C.; Le, H. N.; Tuan, A. V.; Szabo, G. Selective skeletal isomerisation of n-butenes over ferrierite catalyst: Further studies on the possible mechanisms. J. Mol. Catal., A 1997, 123, L1. (14) Mooiweer, H. H.; de Jong, K. P.; Kraushaar-Czarnetzki, B.; Stork, W. H. J.; Krutzen, B. C. H. Skeletal isomerisation of olens with the zeolite ferrierite as catalyst. Stud. Surf. Sci. Catal. 1994, 84, 2327. (15) Simon, M. W.; Suib, S. L.; OYoung, C.-L. Synthesis and Characterization of ZSM-22 Zeolites and Their Catalytic Behavior in 1-Butene Isomerization Reactions. J. Catal. 1994, 147, 484. (16) Can izares, P.; Carrero, A.; Sa nchez, P. Isomerization of n-butene over ferrierite zeolite modied by silicon tetrachloride treatment. Appl. Catal., A 2000, 190, 93. (17) van Donk, S.; Bus, E.; Broersma, A.; Bitter, J. H.; de Jong, K. P. Butene skeletal isomerization over H-ferrierite: A TEOM and in situ IR study on the role of carbonaceous deposits and the location of Brnsted acid sites. Appl. Catal., A 2002, 237, 149. (18) Laxmi Narasimhan, C. S.; Thybaut, J. W.; Marin, G. B.; Denayer, J. F.; Baron, G. V.; Martens, J. A.; Jacobs, P. A. Relumped single-event microkinetic model for alkane hydrocracking on shape-selective catalysts: Catalysis on ZSM-22 pore mouths, bridge acid sites and micropores. Chem. Eng. Sci. 2004, 59, 4765. (19) Seo, G.; Jeong, H. S.; Jang, D.-L.; Cho, D. L.; Hong, S. B. The role of carbonaceous deposits in the skeletal isomerization of 1-butene over ferrierite zeolites. Catal. Lett. 1996, 41 (3-4), 189. (20) Xu, W.-Q.; Yin, Y.-G.; Suib, S. L.; OYoung, C.-L. Coke Formation and Its Effects on Shape Selective Adsorptive and Catalytic Properties of Ferrierite. J. Phys. Chem. 1995, 99, 758. (21) Barri, S. A. I.; Walker, D. W.; Tahir, R. Isomerisation of olens. European Patent, EP0247802, 1987, assigned to BP Company. (22) Grandvallet, P.; de Jong, K. P.; Mooiweer, H. H.; Kortbeek, A. G. T. G.; Kraushaar-Czarnetzki, B. Process for the conversion of a feedstock comprising linear olens. European Patent, EP0501577, 1992, assigned to Shell. (23) Byggningsbacka, R.; Lindfors, L.-E.; Kumar, N. Catalytic Activity of ZSM-22 Zeolites in the Skeletal Isomerization Reaction of 1-Butene. Ind. Eng. Chem. Res. 1997, 36, 2990. (24) Emeis, C. A. Determination of Integrated Molar Extinction Coefcients for Infrared Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts. J. Catal. 1993, 141, 347.

(25) Baerlocher, Ch.; Meier, W. M.; Olson, D. H. Atlas of Zeolite Framework Types; Elsevier Science: New York, 2001. (26) Trombetta, M.; Busca, G.; Rossini, S.; Piccolo, V.; Cornaro, U.; Guercio, A.; Catani, R.; Willey, R. J. FT-IR Studies on Light Olen Skeletal Isomerization Catalysis: III. Surface Acidity and Activity of Amorphous and Crystalline Catalysts Belonging to the SiO2-Al2O3 System. J. Catal. 1998, 179, 581. (27) Wichterlova , B.; Tvaru z kova , Z.; Sobal k, Z.; Sarv, P. Determination and properties of acid sites in H-ferrierite: A comparison of ferrierite and MFI structures. Microporous Mesoporous Mater. 1998, 24, 223. ` ejka, J. Multinuclear MQMAS NMR (28) Sarv, P.; Wichterlova , B.; C Study of NH4/Na-Ferrierites. J. Phys. Chem. B 1998, 102, 1372. (29) van Donk, S.; Bus, E.; Broersma, A.; Bitter, J. H.; de Jong, K. P. Probing the Accessible Sites for n-Butene Skeletal Isomerization over Aged and Selective H-Ferrierite with d3-Acetonitrile. J. Catal. 2002, 212, 86. (30) O. Kresnawahjuesa, R. J.; Gorte, D.; de Oliveira, L. Y.; Lau, A. Simple, Inexpensive, and Reliable Method for Measuring Brnsted-Acid Site Densities in Solid Acids. Catal. Lett. 2002, 82 (3-4), 155. (31) Platon, A.; Thomson, W. J. Quantitative Lewis/Bro nsted Ratios Using DRIFTS. Ind. Eng. Chem. Res. 2003, 42, 5988. (32) Asensi, M. A.; Mart nez, A. Selective isomerization of n-butenes to isobutene on high Si/Al ratio ferrierite in the absence of coke deposits: Implications on the reaction mechanism. Appl. Catal., A 1999, 183, 155. (33) Houz vic ka, J.; Ponec, V. Rebuttal to the Comments of M. Guisnet et al. on Skeletal Isomerization of Butene: On the Role of the Bimolecular Mechanism. Ind. Eng. Chem. Res. 1998, 37, 303. ` ejka, J.; Wichterlova (34) C , B.; Sarv, P. Extent of monomolecular and bimolecular mechanism in n-butene skeletal isomerization to isobutene over molecular sieves. Appl. Catal., A 1999, 179, 217. (35) Villegas, J. I.; Kangas, M.; Byggningsbacka, R.; Kumar, N.; Salmi, T.; Murzin, D. Yu. Skeletal Isomerization of 1-Butene: A Thorough Kinetic Study over ZSM-22. Catal. To day2008, 133135, 762769. (36) Kangas, M.; Villegas, J.; Kumar, N.; Salmi, T.; Murzin, D. Yu; Sandelin, F.; Harlin, E. Mechanism of the skeletal isomerisation of linear butenes over ferrierite: Analysis of side reactions. Catal. Today 2005, 100, 363. (37) Bortnovsky, O.; Sazama, P.; Wichterlova, B. Cracking of pentenes to C2-C4 light olens over zeolites and zeotypes: Role of topology and acid site strength and concentration. Appl. Catal., A 2005, 287, 203. (38) Martens, J. A.; Jacobs, P. A. Introduction to Acid Catalysis with Zeolites in Hydrocarbon Reactions. Stud. Sci. Surf. Catal. 2001, 137, 633. (39) Bhattacharya, D.; Sivasanker, S. A Comparison of Aromatization Activities of the Medium Pore Zeolites, ZSM-5, ZSM-22, and Eu-1. J. Catal. 1995, 153, 353. (40) Corma, A.; Miguel, P. J.; Orchille s, A. V. Product selectivity effects during cracking of alkanes at very short and longer times on stream. Appl. Catal., A 1996, 138, 57. (41) Meusinger, J.; Corma, A. Inuence of Zeolite Composition and Structure on Hydrogen Transfer Reactions from Hydrocarbons and from Hydrogen. J. Catal. 1996, 159, 353. (42) Simpson, M. F.; Wei, J.; Sundaresan, S. Kinetic Analysis of Isobutane/Butene Alkylation over Ultrastable H-Y Zeolite. Ind.Eng. Chem. Res. 1996, 35, 3861. (43) van Donk, S.; Bitter, J. H.; de Jong, K. P. Deactivation of solid acid catalysts for butene skeletal isomerisation: On the benecial and harmful effects of carbonaceous deposits. Appl. Catal., A 2001, 212, 97. (44) Meunier, F. C.; Domokos, L.; Seshan, K.; Lercher, J. A. In Situ IR Study of the Nature and Mobility of Sorbed Species on H-FER during But-1-ene Isomerization. J. Catal. 2002, 211, 366. (45) van de Runstraat, A.; Kamp, J. A.; Stobbelaar, P. J.; van Grondelle, J.; Krijnen, S.; van Santen, R. A. Kinetics of Hydro-isomerization of n-Hexane over Platinum Containing Zeolites. J. Catal. 1997, 171, 77. (46) Laxmi Narasimhan, C. S.; Thybaut, J. W.; Marin, G. B.; Jacobs, P. A.; Martens, J. A.; Denayer, J. F.; Baron, G. V. Kinetic modeling of pore mouth catalysis in the hydroconversion of n-octane on Pt-H-ZSM-22. J. Catal. 2003, 220, 399. (47) Sastre, G.; Chica, A.; Corma, A. On the Mechanism of Alkane Isomerisation (Isodewaxing) with Unidirectional 10-Member Ring Zeolites. A Molecular Dynamics and Catalytic Study. J. Catal. 2000, 195, 227. (48) Domokos, L.; Lefferts, L.; Seshan, K.; Lercher, J. A. Applied Molecular Simulations over FER-, TON-, and AEL-Type Zeolites. J. Catal. 2001, 203, 351.

ReceiVed for reView January 15, 2008 ReVised manuscript receiVed April 23, 2008 Accepted May 7, 2008 IE800061Q