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Ind. Eng. Chem. Res. 2008, 47, 5402–5412

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, Åbo Akademi UniVersity, FI-20500 Turku/Åbo, 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 efficient in the test reaction, their deactivation behavior differed substantially. H-FER exhibited significantly 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, confirming 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 refining 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 today’s refineries include fluid 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 refinery process efficiencies 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 olefins, by oligomerization into fuels and lubes, or by isomerizing linear C4 and C5 olefins into their branched, and more valuable, counterparts. The production of refinery-deficient 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 finding 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 mechanism3–15 and the beneficial effect of coking on reaction selectivity.3–5,8,13,15–20 Zeolites with channel-type structure and pore diameters between 4 and 5.5 Å 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.fi. † Åbo 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 first 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 Teflon-lined autoclave at 433 K for 72 h. The synthesized material was filtered, 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 final

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

Cracking Experiments. The spectra were recorded at 373 K using a spectral resolution equal to 2 cm-1. Isobutene has been placed inside the micropore space of the zeolites. By adding an evaporator to the experimental setup. 15.4. respectively.4 and 40 h-1. and the specific surface areas were measured by the nitrogen adsorption method (Sorptometer 1900. the reactant flow 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. When the catalyst bed had reached reaction temperature. the cracking behaviors of the linear 1-octene and the heavily branched diisobutene isomers were also studied. Vol. Baker) was added to recover the soluble part of the coke. although their bulk Al contents differ quite a lot. Res. Coke Characterization.5 to 20 h revealed an additional 80 µmol/g (∼30%) of medium-strength Brønsted sites in H-FER. 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. and the Dubinin method was used to calculate the specific surface area. Carlo Erba Instruments). Quantitative results were calculated from the integrated absorbance areas of the corresponding peaks using the integrated molar extinction coefficients of Emeis. 3. . were used to identify Brønsted (BAS) and Lewis acid sites (LAS).7 Å. equipped with an online gas-phase autosampler. Regeneration of the used zeolite catalysts was done by in situ burning of the deposited coke. and the other consists of eight-membered rings (8 MR) with dimensions 3. The structure and phase purity of the tested zeolites were determined by an X-ray diffractometer (Phillips PW 1820).6 × 5. After filtration and separation of the phases. and flakelike crystals were observed for FER.Ind. The TON structure is unidimensional and has 10 MR pores with dimensions of 4. Chem. NH4-FER was obtained from Zeolyst International (CP 914) and was transformed into proton form (H-FER) by a step calcination procedure in a muffle oven. Spectral bands at 1545 and 1450 cm-1. No.1 × 0. The grouping limits were determined by injecting a mixture of n-paraffins and assuming that the straigh-chain alkane is the first peak to appear for each group.2 × 5. Samples of the zeolites were pressed into thin self-supporting wafers (8 mm) of approximately 10 mg. the reactant and nitrogen were introduced and the first sample was taken after 10 min on stream.24 The acidity was also measured by temperature-programmed desorption of NH3 (NH3-TPD).5%. typical of 1-D crystal structures. Catalyst Structures and Characterization. while the amount of BAS stayed mostly unchanged for H-TON. and parts of the host structures and the guest molecule are represented by 70% of their CPK volumes. The figure depicts the 10 MR pores of the frameworks viewed along [001]. and feedback for heating control was provided by a thermocouple inside the catalyst bed.1 µm for TON. Isomerization Experiments. Results and Discussion 3. Ferrierite (FER) is a two-dimensional zeolite containing two perpendicularly intersecting channel systems. The reactor was placed in an oven. 2. crushed. and weight hourly space velocities (WHSVs) between 6 and 88 h-1.3. and octenes when calculating the results.25 The morphology of the two zeolites was studied with scanning electron microscopy (SEM).25 One channel consists of 10-membered rings (10 MR) with dimensions of 4. equipped with a flame-ionization detector and a capillary column (HP-PLOT Al2O3 50 m × 530 µm × 15 µm). Pyridine was adsorbed at 373 K for 30 min and then desorbed by evacuation at different temperatures (523. 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. Both catalysts saw a dramatic increase in the amount of LAS found when saturated at elevated temperatures. 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. The heavier compounds could not be sufficiently separated and were grouped according to carbon number into hexenes. 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. Surprisingly. and the bed was kept in place with quartz wool and sand.5 × 4.1 µm for FER and 1 × 0. The catalysts were outgassed at 473 K prior to the measurements. temperatures ranging from 523 to 673 K. 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.T. 2008 5403 calcination of the sample at 823 K for 10 h was carried out in a muffle oven to obtain the proton form H-ZSM-22 (H-TON) zeolite. approximately 10 mL of dichloromethane (J.26–28 The theory of severely diffusion-controlled transport of pyridine into the zeolite pores was. the choice of pyridine as a probe molecule for ferrierite type materials has been challenged. together with a packing of glass beads in front of the catalyst bed. 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. Graphical representations of the two structures are shown in Figure 1. After completed reaction.5 g of catalyst particles (pelletized. The effluent from the reactor was passed through a heated line to the gas chromatograph (Agilent Technologies 6890N). 623. provided a uniform flow of gases to the bed and preheated the reactants. analysis of the organic phase with GC-MS (Agilent Technologies 5973N) was made. The structures of the coked zeolites were destroyed by treatment in 2 mL of 40% hydrofluoric acid (Merck) for every 0.4 Å. The experiments were carried out with reactant partial pressures varying from 0.) as a probe molecule. a. pentenes. These. However. whereas the crystals of TON were shaped like needles. and including. The reactor was packed with roughly 0. and 723 K) to obtain the distribution of acid site strengths.r. A fixed-bed minireactor operating in the vicinity of atmospheric pressure connected to a gas chromatograph (GC). The sample was adsorbed with ammonia at 473 K and later flushed with helium at the same temperature. The GC column was able to separate all components up to. The bulk silicon-to-aluminum ratio was determined by X-ray fluorescence (Siemens SRS 303). 47. the Brønsted acidities measured by Py-FTIR for the two zeolites were very similar (180 vs 178 µmol/g).. therefore.25 mg of used catalyst. A heating rate of 20 K/min was used.0 atm. 2.8 Å. Performing the adsorption at 473 K and prolonging the adsorption time from 0.1 to 1. Following dissolution of the zeolite structure.1.2. Eng. The typical crystal sizes approximated from SEM micrographs were 1 × 1 × 0. heptenes. tested by increasing the adsorption temperature and time. illustrating the limited space available to the reactants and products. and crystal shape and size was studied using scanning electron microscopy (Cambridge Leica 360). was used in the study. The results of the characterizations are summarized in Table 1. 2. The acidity of the investigated catalysts was measured by infrared spectroscopy (ATI Mattson FTIR) using pyridine (>99. and sieved to 100-125 µm).

although the quantitative results by NH3-TPD differed significantly from the ones obtained by Py-FTIR. and they both exhibited a NH3 desorption maximum at 723 K. indicating that the samples have similar distribution acid site strengths. 3. such as temperature-programmed desorption-thermogravimetric analysis (TPD-TGA) with n-propylamine. 2008 Figure 1. 15.5404 Ind. The amount of acid sites measured by NH3-TPD for the two tested catalysts were also very close (590 and 560 µmol/g. indicating that the use of Emeis’ extinction coefficients for FER results in too low concentrations. for FER and TON.. Chem.. A comparison between reported extinction coefficients in a recent publication31 also suggests that the coefficients are not portable from one material to another or from one IR technique to another. The majority of the ammonia desorbed between 573 and 773 K. for both catalysts. The FER zeolite used (Zeolyst CP 914) has also been studied using other acidity measurement techniques. and trans-2-butene) can be considered the reactant because double-bond migration in 1-butene is significantly faster than skeletal isomerization or any other .2.30 and total Brønsted acid site concentrations between 350 and 530 µmol/g have been obtained. Res.29. Although 1-butene is the reactant initially introduced into the reactor. Graphical representation of isobutene in the 10 MR channels of FER and TON: (a) FER and (b) TON. 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. Vol. cis-2-butene. Eng. 47. Isomerization of n-Butene. n-butene (i. No.e. respectively). 1-butene.

2. therefore. O.33 Skeletal isomerization of pentene is much easier to catalyze than branching of butene. somewhat similar to the codimerization route. WHSV ) 6-44 h-1.1 2. Three main reaction mechanisms for skeletal isomerization of linear butenes into isobutene have been proposed in the literature. the monomolecular. thus. also known as the autocatalytic route.8.7.1-1.3 suggested a pseudomonomolecular mechanism. If the main route to isobutene is the classical bimolecular one.15 the pseudomonomolecular. the pseudomonomolecular reaction mechanism has been heavily criticized.0 X-ray Fluorescence Si/Al 30 Nitrogen Physisorption specific surface area. precluding the pseudomonomolecular and codimerization routes as the predominant ones for both tested zeolites. No. 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%.4 177. one linear and one branched butene combine to form a trimethylpentene.13. which is usually associated with monomolecular branching via opening of the protonated cyclopropane transition state. Although an increase in conversion with increasing n-butene partial pressure is observed. Both routes involve carbenium ions as active sites and. equilibrium among the pentene isomers was always reached for the experimental conditions employed in this work.7 91. (mL/g) 0. pHC ) 0.5 a Desorbing between 523 and 623 K.6..4 the initial rate of isomerization in this work is almost constant (zero order in butene) for highly diluted feeds. Isobutene Formation. 9..8.4 8.12.5 2. The mechanism avoids the thermodynamically unstable primary product carbenium ion. H-FER.0 atm. In the classical bimolecular proposal.7 6. The bimolecular mechanism proposals can be further subdivided into two separate routes. the apparent rate of isobutene formation over nondeactivated H-FER is actually decreasing.085 LAS 10. the classical bimolecular6. 47.6 40 295 0.141 H-TON BAS 11.3 3.Ind. 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. The sites for this.4. improbable that the pseudomonomolecular reaction or bimolecular codimerization mechanisms would operate only for skeletal isomerization of butene but not for pentene. The initial rate of n-butene conversion and isobutene formation versus butene relative partial pressure is illustrated in Figure 3. Guisnet et al. avoid formation of unstable primary carbenium ion-like reaction intermediates or transition states but proceed instead through energetically more Figure 3. 673 K. Res. (m2/g) 432 micropore volume. studied over H-FER. Rates of n-butene conversion (9) and isobutene formation (•) as a function of reactant relative partial pressure (pn-butene/ptot). n-butene dimerizes into dimethylhexene that undergoes further isomerization and finally cracks into one isobutene and one n-butene. WHSV ) 12 h-1. 623 K.14 and the codimerization9–11 paths. H-TON and H-FER: 2.5 and Andy et al.12 n-pentene was in this study isomerized much faster than n-butene. and as the 1-butene partial .8. supposedly very active and selective. At high n-butene partial pressures. In line with previous studies. The possible pressure effect on product yield and selectivity was. TOS ) 10 min. Chem. 15.5 and the bimolecular6.9–11. As shown in Figure 2.(n-butene)out (1-butene)in (product)out (1-butene)in Figure 2. × 100% (1) (2) Yield ) Selectivity ) × 100% × 100% (product)out (1-butene)in . The monomolecular route involves only one n-butene molecule and converts it exclusively into isobutene. in order to explain the apparent change in mechanism with increasing time-onstream observed in many studies. T ) 623 K. Nevertheless.12 and there is a general consensus that branching of molecules with five or more carbons occur monomolecularly. probably both monomolecular and bimolecular mechanisms are operating.2 sum 179. chemical reaction involving 1-butene.32.7 19.12. route are docked carbenium ions located inside the zeolite pores. is potentially the more selective of the two bimolecular pathways. thus. TOS ) 46 h.4 74. b Desorbing between 623 and 723 K. an increase in reactant partial pressure should result in significantly higher rates of isobutene formation.6. Characterization of the Zeolites Used H-FER FTIR of Adsorbed Pyridine (µmol/g) BAS LAS weaka 10. 573 K. moreover. Vol.14 reaction routes. theoretically possible. Eng. closed symbols. c Remaining after desorption at 723 K. ptot ) 1. n-Pentene-isopentene equilibrium. which cracks into two isobutene molecules. The codimerization route.35 In agreement with the findings of Domokos et al.1 c strong 108. 2008 5405 Table atm. It is. favorable secondary carbenium ions only.6 mediumb 60. and 100% selectivity is. In the codimerization scheme.(n-butene)out (3) 3. A constant equilibrium among the linear butene isomers gives the following definitions: Conversion ) (1-butene)in .7 2. open symbols.

A small but rapid increase during the first hours. open square.5406 Ind. The unwanted reactions yielding olefinic byproduct . The yield of the desired product at 573 K also stays higher for H-FER throughout the experiments. pHC ) 0. 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. H-FER. Relative isobutene yield. WHSV ) 6 h-1. solid circle. 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. which could be the reason that prolonged reaction times are needed for highly selective operation of H-TON. With the exception of the runs performed at 523 K. The relative isobutene yield. pressure approaches zero (the dashed lines in Figure 3 are extrapolated lines). whereas H-TON exhibits higher isobutene yields at longer times on stream at 673 K. The different deactivation behavior is also. left-facing triangle. the overall rate of butene conversion and isobutene formation meet. The figure illustrates the differences in time-onstream behavior with regard to isobutene yield for the two tested zeolites. WHSV ) 44 h-1. pHC ) 0. A direct comparison of isobutene yield at 573 and 673 K is shown in Figure 5. defined as the yield at time t divided by the initial yield measured at TOS ) 10 min. WHSV ) 6 h-1.5 atm. 523 K. causing an increase in the apparent rate of isobutene formation and selectivity. the isobutene yield over H-TON more than doubles. 623 K. Chem. 15. circle. is typical for H-FER. followed by an almost linear change in isobutene yield. No. 2008 Figure 4. Vol. 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. (b) T ) 673 K. Res. H-TON. upward-facing triangle. 673 K. H-TON. square. during the first 25 h. H-FER. once more. WHSV ) 12 h-1. which is close to previously reported values of 644 and 686 mmol/(gcat h) for FER and similar experimental conditions. Olefinic Byproduct Formation. The apparent activation energy for H-FER seems to be significantly lower than that for H-TON. Evolution of isobutene yield: (a) T ) 573 K. Figure 5. solid square. (b) H-TON.2. Eng. as the initial yield at 523 K for H-FER is already 16 mol %. open circle.2.5 atm: (a) H-FER. 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. As the catalyst deactivates. for the experiments carried out with a WHSV value of 12 h-1. 573 K. especially in cases where the thermodynamic equilibrium between butene isomers is established. The initial yield of isobutene is again always higher for H-FER than for H-TON. evident from Figure 5. while the initial yield over H-FER for the same conditions is already close to 30 mol %.. At 673 K. The initial rate of 4 g/(gcat h) corresponds to 71 mmol/(gcat h). 3. whereas only 4 mol % isobutene is observed over H-TON. the apparent rate of isobutene formation with a 1:9 dilution is continuously decreasing with time-onstream with hardly any increase in selectivity. is shown in Figure 4. Beside the desired isobutene. from 17 to 36 mol %. the overall conversion decreases. However. The needlelike crystals of TON have larger relative contribution of external (nonselective) sites than the flakelike crystal structure of FER. whereas the change in yield with time-on-stream is even more for H-TON. large amounts of unsaturated byproduct are also formed. 47. WHSV ) 44 h-1. Both zeolites exhibit decreasing trends in isobutene yields with TOS at the lowest temperature.

.0 8. For modeling purposes.9 0. For H-FER.2 673 K 46 h 0.0 0.5 37.4 20. If pentene and propene were primarily produced by cracking of octene.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.0 0.4 9. Byproduct formation was the most pronounced in the experiments with long residence times and elevated reaction temperatures. especially at 673 K. the main reaction routes need to be identified. The reaction network was checked by estimating the fraction of hexene produced via cracking of surface-bound nonene.5 13.2 24.3 1.9 46 h 0.7 16. monodimensional 10 MR zeotypes and zeolites.6 12. translating into superior initial selectivites compared to those of H-TON.1 1. shown in Figure 8. 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.9 22.0 32.8 6.6 0. is even clearer.7 3.0 1. the linear relationship between heptene and propene.3 3. Eng.Ind. the C3)to-C5) ratio is a good test of the reaction network.0 2.2 27. WHSV ) 6 h-1.6 2.5 atm temperature TOS LHCa ethene propane propene isobutane n-butane n-butene isobutene pentenes hexenes heptenes octenes a 573 K 10 min 0.5 0. Proposed Reaction Scheme: MH ) Methylheptene.1 16. The main behavior with regard to product distribution and time-on-stream trends was roughly the same for both catalysts.2 30.3 2.7 1.1 0. 2008 5407 Scheme 1. The plots of hexene versus propene yields exhibit a clear bending at higher conversions. As propene takes part in most of the reactions yielding byproduct. pHC ) 0.4 23.37 and propene and ethene have been observed as primary products over FER when introducing 1-pentene as a reactant under similar reaction conditions.6 12.3 10 min 0. Res.1 1. H-TON exhibits higher isobutene selectivites and yields than H-FER after 46 h. Product Distribution (in mol %) for H-TON. are both typically around 1-7 mol % each.7 2.1 0.3 2.7 2. the isobutene selectivities for H-TON increase significantly with time-on-stream. H-FER has 5-8 mol % higher yields of both the reactant and product butenes. with a reaction order of close to zero with regard to butene.4 3.1 0.2 LHC ) methane + ethane. as the catalyst deactivates.5 0.6 40.5 1. pHC ) 0. The product distributions for the experiments carried out with a WHSV value of 6 h-1 are given in Tables 2 and 3. thus.1 2.7 0.9 1.0 8.7 23.2 6.3 3.3 2. Table 3.2 21.0 1. in some cases accounting for more than one-third of the total yield. while the rest of the components in the system exhibited decreasing tendencies in yields with prolonged operation time.5 16.9 5. The maximum amounts of ethene obtained in this work were 4 mol % for H-FER and 7 mol % for H-TON. However. and in the experiments carried out at 623 and 673 K.9 10.8 10 min 0.2 5. No. include disproportionation of butene into propene and pentene and various dimerization and oligomerization reactions.1 2.6 10 min 0.0 10 min 0.0 4.0 1.6 40.3 12. WHSV ) 6 h-1.8 3. which will be discussed in detail in an accompanying paper.4 37. The dramatic increases in isobutene yields and selectivites coincide with similar decreases for disproportionation products.8 4.5 atm temperature TOS LHC ethene propane propene isobutane n-butane n-butene isobutene pentenes hexenes heptenes octenes a a 573 K 10 min 0. have been found to catalyze pentene cracking via monomolecular β-scission.3 0.5 3.1 0. 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.4 0.1 1. The pentene-to-propene ratios for fresh catalysts are approximately the same for both zeolites. The yield of octene as a function of propene is shown in Figure 6d.5 6.8 6.9 4.9 7.3 4.4 5.4 32.9 673 K 46 h 0. on the other hand.0 6.0 0.8 0.1 2.6 3.7 0. 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.2 2.7 21. which are dimers of propene and codimers of propene and butene. Scheme 1 shows that hexene can be formed either from dimerization of propene or from cracking of an adsorbed C9 species.0 16. The side-reactions taking place in butene skeletal isomerization over H-FER were studied by Kangas et al.7 LHC ) methane + ethane.1 5.2 28. including proton-form FER.5 0.2 1.3 32.0 3.5 5.6 1. Vol. However.2 2.4 5. respectively. This indicates that heptene is rapidly formed from propene and butene. the molar ratio between them would be around 1.1 18. For fresh catalysts. Propene and pentene were always the most abundant byproducts.2 1.0 0. Cracking of pentene involves a primary carbenium ion-like intermediate and might. slightly higher than that for H-TON. although they behave quite differently with regard to propene. DMH ) Dimethylhexene.36 and the proposed reaction network is reproduced in Scheme 1.9 5. and TMP ) Trimethylpentene Table 2.4 1.1 13. Figure 7 further illustrates the differences in pentene and propene yield for the two catalysts at the highest reaction temperature of 673 K.7 25.1 0.6 0.0 0. Product Distribution (in mol %) for H-FER.5 16.6 The yields of hexene (Figure 6b) and heptene (Figure 6c). 47.0 4.5 623 K 46 h 0.0 11.6 5.6 6.4 0.7 13.2 0.0 0. Chem.2 13. with increases in butene and octene yields with TOS. 15..8 12.5 2.9 46 h 0.5 29.5 1. the ratio is initially increasing for H-FER and approaches a constant value. but while it stays rather constant for H-TON.4 0. which suggests an additional reaction involving propene and hexene. and it behaves differently compared to the other pseudocomponents.7 13.0 3. be more difficult to catalyze than the rest of the reactions represented in Scheme 1.4 3.0 17.5 32. Heptene.7 4. displays nearly linear dependencies with regard to propene.9 13.1 623 K 46 h 0.6 19. As evident from Figures .5 36. The yield of pentene versus the yield of propene for the n-butene experiments over H-TON is illustrated in Figure 6a.9 33.8 6.5 6.4 2. H-FER exhibited similar trends with the exception that the pentene yields at 623 and 673 K presented maxima.

573 K.5 atm. the fraction is very close to 1 and almost independent of temperature or TOS. the fraction always exceeds 1. O. The fraction of hexene produced from nonene as a function of temperature and time-on-stream is shown in Figure 9. pHC ) 0.5 atm. Figure 8. 47. WHSV ) 6-44 h-1. O. pHC ) 0. 15. 573 K. 6a and 7. Figure 7. 2. H-FER. pHC ) 0. H-TON.5 atm. T ) 573-673 K. with larger portions of the hexene formed from nonene at lower temperatures. For H-FER. For weight hourly space velocities g 44 h-1. ) ) ) ( ) ) ″ C3 ″ ) C) 3 + C3 . WHSV ) 6-44 h-1.xC6 + 2 1 . Chem. Pentene yield versus propene yield for H-FER (2) and H-TON (9): T ) 673 K. the fraction is steadily increasing with time-on-stream and it exhibits an obvious dependence on reaction temperature. Res. Vol. 623 K. 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. 2008 Figure 6. For H-TON.x C6 + C7 ) ) ″ C5 ″ ) C) 5 + C2 + xC6 (4) (5) where x denotes the fraction of hexene formed from nonene (Scheme 1). the observed ratios can differ significantly 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. Heptene yield versus propene yield. Major byproduct distribution. For lower weight hourly space velocities (not shown). 623 K. 673 K. suggesting that no changes in predominant routes to byproduct occur with elevated temperature or prolonged operation time. and consequently longer residence .C2 . The sum of C3 and C5 molecules is defined in the following manner. 2. WHSV ) 6-44 h-1. Eng. 673 K..5408 Ind. 9. 9. No.

Figure 10. The creation of coke is usually considered to involve many consecutive steps. 673 K. While H-FER exhibits the expected order of the ratios if no severe spatial restrictions are present. in which propene and butene act as hydrogen acceptors and transform into their saturated counterparts. This indicates that the transition states in bimolecular hydride transfer involving isobutene are significantly more constrained in the channels in TON than in FER. alkylation of the formed monoaromatic. No. the ratio should be above the thermodynamic value. 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. Accompanying the formation of each aromatic ring are three bimolecular hydrogen transfer reactions. Eng.7 aromatization. the fraction of hexene produced from nonene cracking decreases for both zeolites. Although TON has larger pores than FER. transformation into monoaromatics through bimolecular hydride transfer. T ) 673 K. 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. 2. Examples of the olefin-to-paraffin ratios for the C3 and C4 molecules in H-FER and H-TON are shown in Figure 10. pHC ) 0. producing hydrogenated and dehydrogenated products. and n-butene and isobutene are present in sufficient amounts. 2.41 Hydride transfer is generally thought of as the rate-limiting step in hydrogen transfer. spherical cavities of 6-7 Å are formed.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. the ratio should be around 0.8 for the conditions used in this work. If the self-hydrogenation is controlled thermodynamically. and the bimolecular elementary step exhibits sterical constraints in many zeolites. deactivation occurs mainly through formation of coke that covers the active sites and/or blocks the zeolite channels. The hydride abstraction step has been reported to be sterically more hindered than olefin addition. iso-C4. The formed biaromatic coke can then be further transformed into triaromatics. WHSV ) 44 h-1.16 and this seems sufficiently large to accommodate at least some of the transition states needed for hydrogen transfer to isobutene.5 atm. Chem. times. At the intersection between the 8 MR and 10 MR pores in FER. due to the much faster reaction of branched molecules. Res.. O. 573 K. A somewhat more accurate estimation of sterical constraints in butene isomerization is the ratio of isobutane to n-butane (i/n). therefore. n-C4. Vol. In solid acid catalyzed reactions of hydrocarbons.Ind. C3.42 and the correlation between paraffins and olefins is. hydride transfer. and further ring closure of the alkyl-substituted monoaromatic into a bicyclic compound that in turn undergoes further hydrogen transfer reactions to finally produce a biaromatic molecule. The reaction consists of protonation. 9. Olefin-to-paraffin ratios.16 If the hydrogen transfer reactions are kinetically controlled. O. cyclization. hydride transfer to isobutene seems more restricted in H-TON than in H-FER. 9. Fraction of hexene produced through nonene cracking: (a) H-FER and (b) H-TON. and deprotonation elemementary steps. Hydrogen Transfer Reactions. pHC ) 0. Houz ˇ- . 2008 5409 Figure 9.5 atm: (a) H-FER and (b) H-TON. Hydrogen transfer involves a net transfer of H2 from one molecule to another.39 and cracking reactions.3. WHSV ) 6 h-1. 3. 15. 623 K.2. oligomerization of smaller olefins to form larger ones. etc. 47. also a convenient way to evaluate pontential shape-selectivity effects.40.

giving ratios well-above 0. 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. and analysis by GC-MS. or three aromatic rings. whereas diisobutene contains three methyl groups. As expected.10 vic ˇ 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. Deactivation and Regeneration.19. 1-Octene has a fully linear skeleton and lacks any side -chains. the coke formed on H-FER was heavier and more aromatic in nature compared to that formed on H-TON. Deactivation by coking always accompanies butene skeletal isomerization.34 0. the disproportionation products account for one-third of the yield when cracking diisobutene over fresh H-TON. High-temperature coke was also less soluble in dichloromethane than deposits formed at lower temperatures. the closest to desired product distribution was obtained when feeding diisobutene. although the relative concentration of isobutene among the butene isomers is decreasing. The tested zeolites could be regenerated by burning the carbonaceous deposits in synthetic air. Cracking of Octene Isomers. and the ratio of branched to linear butane varied around the thermodynamic one. There exists 15 structural isomers of octene. For H-TON.43 The amount of deposits on H-TON was roughly one-half that of H-FER.3. Although isobutene cannot be formed as a primary product from n-octene cracking. a narrowing of the micropores by coke deposits should slow down hydrogen transfer to isobutene more than to n-butene.3–5. ranging from 3 to 4. Still. Cracking of 1-octene produced the least amounts of isobutene. and for H-FER. in the sense that it usually results in higher isobutene selectivities. approximately 2-fold that of H-FER. Diisobutene cracking is usually considered the most facile of the octene isomer β-scission reactions and is theoretically 100% selective to isobutene. including a geminal pair. No clear trends in the nature of the carbonaceous deposits as a function of temperature were observed.14. two. the cracking reaction of diisobutene might also predominantly take place on the outer surface of the zeolite crystals.5410 Ind. 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 first hour of reaction.46 and diffusional resistance47 of mono. A summary of the experimental findings is presented in Table 5.81 0. The amounts of lighter species. together with the results from 1-butene isomerization under comparable conditions.8.08 0.11 0. are probably underestimated.33 46 h 0.13. although the total amount of hydrogen transfer products for H-TON is 2-fold that of H-FER. The ratios of isobutane to n-butane for H-FER exhibited maxima after 10-20 h TOS in all the experiments. If the main effect of coking is increasing the steric constraints for reaction and diffusion. Because of the steric constraints of the branched molecule in the tested catalysts. Eng. although the loss in activity per regeneration is decreasing. For fresh zeolites. since they possess high volatilities and parts of them most likely evaporate with the dichloromethane.and dibranched hydrocarbons in TON. H-FER is more sensitive to reactant octene isomer as far as product distribution is concerned and always exhibited higher yields of isobutene.2. although higher butene partial pressures resulted in more aromatic and less aliphatic coke. After five regenerations. The aliphatic coke family. Toluene and xylenes have also been observed directly by GC in the reactor effluent (see Scheme 1). at least for conditions close to those employed industrially.4. and five times regenerated zeolites are depicted in Figure 11.16 thus decreasing the i/n ratio.5 atm H-FER 10 min 673 K 623 K 573 K 0.44 The most abundant coke species on both H-TON and H-FER were alkyl-substituted naphthalenes. which is in agreement with previous reports for FER catalysts. Isobutane-to-n-Butane Ratios. The sum of C3-C4 hydride transfer products for H-TON is. both zeolites have lost roughly 5 mol % in conversion and isobutene yield.43 0.18.35 The chemical nature of the coke formed in this study was investigated by dissolution of the zeolite structure. WHSV ) 6 h-1. Chem. and the reaction produced mostly propene and pentene. coking has proven beneficial.17. and feeding 1-butene yielded a distribution of products in between the two. such as toluene and xylenes. H-TON is also more selective toward disproportionation. As such. The values for TON and FER zeolites were approximately the same as those obtained in this study (Table 4).36 1. In the same time frame. for all tested reactants. The exact role of the carbonaceous deposits and their mode of formation and location are still subjects of discussion. Vol. losses in activity of approximately 2-3 mol % were observed when either diisobutene or 1-butene were fed as reactants. 3. the olefin product distribution (Table 5) was almost the same for H-FER and H-TON. they behave differently when cracked and when diffusing through the narrow zeolite channels of the medium-pore zeolites. Quantitative measurements of the coke content were obtained by temperature-programmed oxidation.45 steric constraints. extraction with dichloromethane. No.4. and both catalysts regained almost all of their initial activity. There is an ongoing discussion in the scientific literature on the shape-selective effects. 15. the ratio was always decreasing.43 since 8 MR pore structures have been shown to be far more selective toward n-butane than isobutane. . whereas components with two and four aromatic rings seemed to be favored in H-FER. 2008 Table 4.75 0. For H-TON. For most 10 MR zeolites.58 46 h 1.35 0. Overall. mainly consisting of long linear olefins. The distribution of coke components was estimated by approximating the area of the chromatographic peaks to the amount of corresponding compounds.15–17.20.7 and as long as a significant part of the n-butane is formed in the 8 MR channels. When cracking 1-octene. while hydrogen transfer to isobutene was a lot faster than that to n-butene for largepore (12 MR) zeolites. three. pHC ) 0. the i/n ratio obtained in this work for H-FER is approximately twice as high as that for H-TON. the amount of carbon after approximately 50-70 h time-on-stream varied between 6 and 9 wt %. It has been proposed that the 8 MR channels deactivate faster than 10 MR ones. Coke content increased with increasing temperature for both catalysts. Overall. Res.. the isobutaneto-n-butane ratio increases with time-on-stream for H-FER.32.8. Surprisingly. 47. and the isomers chosen in the present study represent the two extremes. equilibrium between the skeletal isomers of butene was observed for H-FER.63 H-TON 10 min 0. made up roughly 50% of the deposits on H-TON and between 20 and 40% of those on H-FER. The results of repeated reactions with fresh and one. an increase in the i/n ratio with TOS seems logical. Mediumpore (10 MR) molecular sieves were found to be the most selective and stable for 1-butene skeletal isomerization. 3.3. This peculiarity can be explained by different deactivation rates of the acid sites in 10 MR and 8 MR pores in FER. the aromatic compounds were distributed equally among species containing one.5 wt %.

their catalytic behavior differed drastically. on the other hand. the cracking experiments support the conclusions of Domokos et al. Acknowledgment This work is part of the activities at Åbo Akademi Process Chemistry Centre within the Finnish Centre of Excellence Program (2000-2011) by the Academy of Finland. WHSV ) 7.73 0. 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. Both zeolites experienced deactivation through coking during the experiments. WHSV ) 44 h-1.Ind. is gratefully acknowledged. The tested zeolites were easily regenerated by burning of the carbonaceous deposits in synthetic air. no changes in isomerization efficiencies were observed in this case. and both catalysts regained almost all of their initial activity. for the two zeolites and all the reactants is compared in Table 5.63 c H-FER 19 18 46 1 96 1. Res. WHSV ) 6.18 1.. . No.07 0. Coke belonging to both aliphatic and aromatic families was detected.5 atm: (a) H-FER and (b) H-TON. Although the acidities and pore dimensions of the two zeolites were similar. Chem. For the conditions used in this study. while the bimolecular paths of butene were largely responsible for byproduct formation. At the same time. yielding propene and pentene. for both tested zeolites. and the hydrogen transfer reaction of isobutene was. the efficiency of H-FER is close to double that of H-TON.06 1. the coke formed on H-FER was heavier and more aromatic in nature. TOS ) 15 min. Conclusions Both the H-TON and H-FER zeolites used in this study have proven to be efficient catalysts in n-butene skeletal isomerization.0 h-1. ) 4. For 1-octene cracking and 1-butene isomerization. and it was also the more stable with time-on-stream of the two catalysts. with total paraffin yields approximately twice that of H-FER.5 h-1. the different deactivation rates of the 8 and 10 MR channels in H-FER could also be observed.50 atm. Financial support from Graduate School in Chemical Engineering for M.44 Yields (mol %) 17 15 41 3 88 1.36 a TOS ) 15 min. the IE value of H-FER is only slightly higher than that for H-TON. isobutene was formed mainly via the monomolecular route.80 0. Eng. confirming previous theoretically calculated structure effects.28 0. Of the two zeolites used in this study. Overall. Vol. has channel intersections large enough to accommodate some of the transition states yielding isobutane.25 atm. but for the case of diisobutene cracking.35 1. Because of the slightly larger pore dimensions of H-TON.39 H-TON 17 16 37 12 83 1.26 0. 47. The steric constraints in the two zeolite structures were assessed from the ratio of paraffins to olefins and the ratio of isobutane to n-butane. 1 order of magnitude faster in H-FER than in H-TON. the conversion mostly stayed unchanged. which supports the theory of consecutive reactions of isobutene forming propene and pentene. The predominant route to byproduct was dispropor- tionation. with roughly 10-30% losses in n-butene conversion after 2 days time-on-stream. 2.15 atm.77 0.66 1-octeneb H-TON 22 27 32 4 98 0. The isomerization efficiency also more than doubled during the first hour on stream. isobutene yield.48 Using applied molecular simulations over FERand TON-type zeolites in siliceous forms. H-TON was more selective toward disproportionation. Repeated reactions with fresh (solid symbols) and 1-5 times regenerated (open symbols) catalysts. pC8 ) 0. pC4 ) 0. when introducing diisobutene into the reactor.06 1. pC8 ) 0.64 0.87 b 1-butenec H-TON H-FER 23 22 35 7 77 1. T ) 623 K. pHC ) 0.5 h-1. The observed product distribution of H-TON was also less sensitive to feed reactant than that of H-FER. Table 5. it was more selective toward hydrogen transfer products. TOS ) 10 min. FER. Taken together. WHSV ) 7.K. 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. conversion. therefore. 2008 5411 Figure 11. •. H-FER exhibited significantly higher initial isobutene selectivities compared to H-TON. 15.11 0. and pentene to propene. Although both tested catalysts deactivated the most when 1-octene was fed as reactant. Comparison of Main Product Distributions over the Fresh Zeolites for the Cracking and Isomerization Experiments. The isomerization efficiency. defined as IE ) iso-C4)/(C3) + C5 ). From the ratios of isobutane to n-butane.

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