Chemical Engineering Science 59 (2004) 1131 1138

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Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 1: experimental measurements
Chi Keng Lee, Sunil Ashtekar, Lynn F. Gladden, Patrick J. Barrie
Department of Chemical Engineering, University of Cambridge, Pembroke Street, Cambridge CB2 3RA, UK Received 15 October 2003; received in revised form 19 December 2003; accepted 6 January 2004

Abstract An experimental procedure to measure the adsorption and desorption kinetics of hydrocarbons in uid catalytic cracking (FCC) catalysts using a tapered element oscillating microbalance is described. It enables adsorption rates to be measured on a timescale of about 1 s. Experiments using n-hexane, n-heptane, n-octane, toluene and p-xylene were performed on both a commercial FCC catalyst and a pure rare-earth exchanged zeolite Y sample under non-reacting conditions (temperatures of 373473 K). Heats of adsorption for these hydrocarbons are reported. The overall adsorption and desorption kinetics are found to depend on carrier gas owrate in cases when adsorption is strong indicating that the length of the catalyst bed can have a signicant in uence on the observed kinetics. However, at high carrier gas owrates the overall adsorption and desorption kinetics do not depend on the amount of catalyst present. It is found that the rates of adsorption and desorption of the hydrocarbons studied are the same for the FCC catalyst as for the pure zeolite Y sample. This means that mass transport in the matrix component of the FCC catalyst is rapid and not a limiting step in the adsorption process for the hydrocarbons studied in this work. ? 2004 Elsevier Ltd. All rights reserved.
Keywords: Adsorption; Di usion; Zeolites; FCC catalysts; Microbalance; TEOM

1. Introduction The uid catalytic cracking (FCC) process in an oil renery is a key unit operation in which heavy hydrocarbon molecules are cracked to form smaller more valuable products. The FCC catalyst particles employed contain zeolite crystallites embedded in a matrix that contains alumina, clay and sometimes silica. The most common zeolite used is rare-earth exchanged zeolite Y, and this component is responsible for the high activity and selectivity of FCC catalysts. The matrix material has some catalytic activity (e.g. in cracking molecules too large to enter the zeolite) and provides attrition resistance. It also acts as a heat sink and can reduce the extent of heavy-metal poisoning of the zeolite component (Venuto and Habib, 1979; Sattereld, 1980; Scherzer, 1991).
Corresponding author. Tel.: +44-1223-331864; fax: +44-1223-334796. E-mail address: patrick barrie@cheng.cam.ac.uk (P.J. Barrie).

There have been a large number of studies on the catalytic performance of zeolites for cracking reactions. For instance, these have explored the in uence of pore structure and Si/Al ratio, characterised the di erent types of acid site that may be present, investigated coking and deactivation, and proposed reaction mechanisms (Corma, 1993; Rabo and Gajda, 1989; Farneth and Gorte, 1995; Bhatia et al., 1989; Karge, 1991; Cumming and Wojciechowski, 1996; Corma and Orchill s, e 2000). Molecular transport within zeolites has also been extensively studied because it can in uence overall reaction rates, and also because of the use of zeolites in separations processes (Karger and Ruthven, 1992; Chen et al., 1994). There have, however, been very few published studies on adsorption and transport properties in commercial FCC catalyst particles that contain matrix material as well as zeolite crystallites. While many workers believe that the cracking reaction in an FCC unit is not limited by di usional e ects (e.g. Chen et al., 1994), there have been suggestions that pore di usion within zeolite Y does in uence the observed activity, even

0009-2509/$ - see front matter ? 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.ces.2004.01.005

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for molecules as small as n-hexane (Williams et al., 1999; Kung et al., 2000). For this reason, it is important to measure the molecular transport rates of hydrocarbons in FCC catalysts. Knowledge of the adsorption and desorption kinetics is important in the FCC process not only in understanding the chemical reactions occurring, but also in the design of the riser (in which adsorption of heavy compounds could in principle be a limiting step) and in the design of the stripper (in which desorption of hydrocarbons of value is desired before the catalyst is sent to the regenerator). While it is expected that the e ective di usion coe cient, De , in the zeolite component is smaller than that in the matrix component, the particle radius, a, of the zeolite crystallites is about one hundred times smaller than the radius of the overall FCC catalyst particle. Because the e ective rate of transport depends on the value of De =a2 for each component present, it is therefore important to see whether the limiting step for molecular transport in FCC catalyst particles occurs in the matrix or zeolite component. Another uncertainty when considering molecular transport in FCC catalysts is that there remains signicant disagreement in the literature over the correct value of di usion coe cient for hydrocarbons in zeolite Y as values di ering by two orders of magnitude have been obtained using di erent experimental techniques for this particular zeolite structure (Karger and Ruthven, 1989; Ruthven, 2000). In this paper, an experimental conguration suitable for measuring fairly rapid rates of adsorption and desorption from FCC catalyst particles is described. The experiments were performed using a tapered element oscillating microbalance (TEOM). This is a form of inertial balance in which mass changes can be found by measuring the natural resonance frequency of a tapered quartz element containing the sample of interest (Patashnick and Rupprecht, 1986). It allows accurate mass measurements to be made rapidly at elevated temperatures under conditions in which the adsorbate vapour passes through the catalyst bed. The ow conditions used, and the fact that the amount of catalyst used is small (typically 60 mg), means that external mass and heat transfer limitations are far less signicant than when using other microbalance techniques. Further, it is possible to measure mass in a TEOM every 0:1 s and so rapid changes can be investigated. While the TEOM was initially developed to measure particulate concentration in a gas (Patashnick and Rupprecht, 1991), its features make it particularly attractive for studying many phenomena in catalysts. It has thus been used to measure equilibrium adsorption isotherms (Zhu et al., 1998, 2001a; Giaya and Thompson, 2002), mass changes during reduction treatment (Rekoske and Barteau, 1997), the kinetics of coking (Liu et al., 1997a; Petkovic and Larsen, 1999; Chen et al., 2000), and the in uence of coke on catalyst activity and selectivity (Chen et al., 1996a, 1997, 1999a; Liu et al., 1997b; Petkovic and Larsen, 2000; van Donk et al., 2002). There have also been attempts to use TEOM results to consider the combined e ects of adsorption, dif-

fusion, reaction and coking (Chen et al., 1999b; van Donk et al., 2001). Despite this work, there have only been a few published studies so far that have taken advantage of the fast-time resolution of the TEOM to measure adsorption or desorption kinetics (Hershkowitz and Madiara, 1993; Chen et al., 1996b, 1999c; Rebo et al., 1997; Zhu et al., 2001b; Alpay et al., 2003) which is the subject of this work. In this paper experimental TEOM results are reported on the adsorption and desorption kinetics of some simple hydrocarbon molecules within a commercial FCC catalyst and a pure zeolite Y sample under non-reacting conditions (temperatures not exceeding 473 K). The aliphatic hydrocarbons investigated were n-hexane, n-heptane and n-octane; these allow the e ects of chain length to be studied. The aromatic hydrocarbons investigated were toluene and p-xylene; these allow comparison with the results on the straight-chain alkanes to be made. In this paper, the experimental conguration is characterised, equilibrium adsorption results are analysed, and qualitative conclusions are drawn from the transient kinetic measurements. Detailed numerical simulations of the rates of adsorption and desorption will be the topic of an accompanying paper. 2. Experimental The catalyst samples were supplied by BP Oil. The commercial FCC catalyst contains rare-earth exchanged zeolite Y in a matrix, and consists of spherical particles of approximately 70 m diameter. A pure rare-earth exchanged zeolite Y was also used for comparison purposes, and this has particle sizes of 0.51 m. Both samples were steamed at 1089 K for 5 h in order to cause ultrastabilisation. This process causes dealumination of the zeolite component, but enhances the overall stability of the catalyst (Sattereld, 1980; McLean and Moorehead, 1991). It was performed in order to give a catalyst with a composition and structure comparable to that found in FCC units, as the steaming mimics the actual conditions experienced in an FCC unit. Surface area measurements were made by analysing nitrogen adsorption data (Gregg and Sing, 1982) after the steaming treatment to check the structural integrity of the samples. The steamed FCC catalyst sample has a BET surface area of 183 m2 =g, of which t-plot analysis estimates 157 m2 =g is due to micropores. The steamed pure zeolite Y sample has a BET surface area of 377 m2 =g, of which t-plot analysis estimates 343 m2 =g is due to micropores. In this paper, the label FCC denotes the FCC catalyst sample, while the label REUSY denotes the pure rare-earth exchanged ultrastable zeolite Y sample. A schematic diagram of the experimental conguration used is shown in Fig. 1. The catalyst was placed at the bottom of the quartz element of a Rupprecht and Patashnick PMA 1500 TEOM. The amount of catalyst used was up to 64 mg for the FCC sample and 32 mg for the REUSY sample. In some cases the catalyst was diluted with quartz

C.K. Lee et al. / Chemical Engineering Science 59 (2004) 1131 1138

1133

He (pretreat) He (carrier)
TC

valve 1 to vent

hydrocarbon saturator
PT

to GC

He (purge)

TEOM
TC

to GC or MS

to vent
Fig. 1. Diagram of the experimental conguration used.

particles. During a typical experiment to measure adsorption and desorption kinetics, the catalyst in the TEOM is rst activated by heating at 623 K in a dry stream of helium pretreat gas. The sample is then cooled to the temperature of interest (373473 K in this work) while maintaining the helium ow, and the balance allowed to equilibrate at this temperature until a stable baseline is obtained. Pneumatic valve 1 is then switched to allow the helium carrier stream containing hydrocarbon vapour to reach the sample. Once equilibrium has been attained (typically after a 60 s duration), the desorption step is performed by switching valve 1 back to its original position so that the sample is once again exposed only to helium pretreat gas. The element resonance frequency, and thus mass, is monitored at all stages of this process, with a time resolution of 0:11 s per data point. All gas ows in the apparatus are controlled by automatic mass ow controllers. The helium owrates used in all experiments was 200 ml=min at STP conditions unless otherwise indicated. The function of the helium purge stream is to ensure that any hydrocarbons desorbing from the catalyst are removed from the balance. The pipes after the saturator were heat traced to ensure that no hydrocarbon condensation took place before the balance. The concentration of the hydrocarbon in the feed gas can be adjusted by changing the temperature of the saturator. A gas chromatograph (GC) equipped with a ame ionisation detector is used to measure the composition of the feed gas. Experiments were performed using di erent hydrocarbon partial pressures in order to measure equilibrium adsorption isotherms on the catalysts. An important part of the experimental protocol is to ensure that the needle valve on the vent outlet from valve 1 is adjusted to ensure that there is no pressure imbalance in the

system when valve 1 is switched. Any pressure imbalance could be detected by the pressure transducer at the inlet to the TEOM. Pressure imbalances need to be avoided during kinetic measurements as mass changes due to variations in the density of gas owing through the TEOM can be comparable to the mass changes that occur during adsorption and desorption, and a pressure imbalance can take many seconds to stabilise. For instance, when measuring the kinetics of adsorption of alkanes in silicalite, Zhu and co-workers ignored the rst 510 s of data because it was a ected by a pressure imbalance (Zhu et al., 2001b). This meant that they were unable to measure rapid kinetic changes using their experimental conguration. Such a limitation is not a problem using our experimental protocol as is demonstrated by the results below. The experimental conguration allows products from the microbalance to be examined by gas chromatography or mass spectrometry (MS). These showed that there was negligible reaction for the hydrocarbons studied under the conditions employed (373473 K). In order to test for reproducibility, and to rule out the possibility of any coke formed a ecting the kinetic measurements, sequences of 510 separate adsorption/desorption experiments were performed on the same catalyst with no regeneration between each step; identical results were obtained in each case. Experiments were also performed using particles of quartz in the balance in order to check that the mass proles obtained re ect adsorption within the catalyst rather than just changes in the gas density in the interparticle space. In principle, it is necessary to subtract the data obtained using quartz from that obtained using catalyst under identical conditions in order to achieve pure adsorption results. However, under the conditions employed it was found that the mass adsorbed was far greater than the mass in the interparticle space and so this correction was not necessary for the results reported in this paper. The apparatus was arranged in such a way that the length of pipe (diameter 1=16 in) between valve 1 and the microbalance is as small as can practically be achieved in order to minimise dead volume. In order to characterise the dead volume, which is necessary for detailed interpretation of the adsorption kinetics, quartz particles were used in the balance and the carrier gas switched from helium to nitrogen while the pressure and temperature were maintained. 3. Results 3.1. Characterisation of dead volume Fig. 2 shows TEOM results when the carrier gas was switched from helium to nitrogen with 60 mg of quartz particles (diameter approximately 70 m) present in the reactor. An increase in mass is observed due to the higher mass of nitrogen compared to helium. At time t = 0, there is a small peak due to vibrations detected by the balance when

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1 0.8 0.6

C.K. Lee et al. / Chemical Engineering Science 59 (2004) 1131 1138

Mass change per gram of catalyst (g/g)

373 K

0.03
398 K 423 K

Mass (mg)

0.02
448 K

0.4 0.2 0 -0.2 -5 0 5 Time (s) 10 15

0.01

473 K

0 0 0.01 0.02 0.03 0.04 0.05 0.06

Partial pressure of p-xylene (bar)

Fig. 2. TEOM results with 60 mg quartz present and a switch from helium gas to nitrogen gas at time t = 0 and owrate 200 ml=min (at STP conditions). The TEOM temperature was 473 K, the line temperature 423 K, and the pressure was 1:33 bar. The solid line is a t to the data to characterise the dead volume present (see text).

Fig. 3. Equilibrium adsorption isotherms for p-xylene in FCC catalyst. The curves are ts to the Langmuir isotherm expression.

pneumatic valve 1 was switched. However, there is no indication of any long-term pressure imbalance when the valve is switched, and it is clear that reliable adsorption kinetics measurements can be measured on timescales of the order of 1 s using our experimental conguration. The total mass change observed under these conditions is 0:723 mg. This corresponds to the balance detecting gas in a volume of 0:89 cm3 . Ideal step behaviour is not observed due to the dead volume in the apparatus between valve 1 and that part of the element in which mass is detected. This volume comprises pipework, the valve to the GC, the pressure transducer, and volume at the top of the TEOM. Under the conditions of this experiment, it can be seen that there is a time lag of 0:8 s before any change in mass is detected, after which the shape of the curve follows a curve that can be tted with an exponential function with time constant 0:96 s1 . This behaviour corresponds to the apparatus behaving as if there was a region of plug ow after valve 1 with volume 3:1 cm3 , followed by a well-mixed region with volume 4:2 cm3 , before gas reaches that part of the element in which mass is detected. The solid line in Fig. 2 is the curve that uses these volumes to model the behaviour. The volumes obtained can then be used to predict what actual gas concentrations will be in the absence of adsorption at other temperature and pressure conditions. This characterisation means that ideal step behaviour need not necessarily be assumed when modelling TEOM results for the uptake of an adsorbate into a catalyst. 3.2. Measurement of equilibrium adsorption isotherms The partial pressure of hydrocarbon in the carrier stream was varied by changing the temperature of the saturator, and the mass adsorbed in the catalyst at equilibrium measured by the TEOM. Experimental results for p-xylene in the FCC catalyst at ve di erent temperatures are shown in Fig. 3.

The curves are ts of the experimental data to the Langmuir adsorption isotherm Mmax KL PHC M= ; (1) 1 + KL PHC where M is the mass adsorbed, Mmax is the amount adsorbed at high pressure, KL is the Langmuir constant, and PHC is the partial pressure of the hydrocarbon. The tted curves show that this isotherm is a reasonable model of the amount adsorbed at equilibrium for this catalyst. Similar quality data and ts were obtained for all the hydrocarbons studied (n-hexane, n-heptane, n-octane, toluene and p-xylene) on both the FCC catalyst and the REUSY sample. In most cases, it was possible to obtain reasonable ts to the data by constraining Mmax to be independent of temperature for the systems studied, though this is not necessarily a requirement for hydrocarbon adsorption in zeolites. It can be seen that TEOM experiments can readily be performed in both the linear region of the isotherm (e.g. at high temperature or low partial pressure) or in the non-linear region where saturation can be approached (e.g. at low temperature or high partial pressure). Heats of adsorption, Hads , in the low coverage limit were calculated from the isotherms using the equation (Ruthven, 1984): d ln KH Hads ; (2) = dT RT 2 where KH is the Henry constant (and thus equals the gradient of the isotherm plots at low coverage). Values of the heats of adsorption, together with the Langmuir parameters obtained, are shown in Table 1. It should be mentioned that there is a reasonably large uncertainty (3 kJ mol1 ) in the heats of adsorption obtained from our TEOM measurements as our experimental conguration is optimised for the measurement of transient kinetics at moderate pressures rather than the amount adsorbed at very low pressures. The values obtained on the linear alkanes are in good agreement with values obtained in the literature on zeolite Y samples in other cation-exchanged forms (Eder and

C.K. Lee et al. / Chemical Engineering Science 59 (2004) 1131 1138 Table 1 Summary of the results obtained from analysis of the adsorption isotherms Adsorbate Catalyst n-hexane FCC Hads (kJ mol1 ) 45 T (K) 373 398 423 448 473 373 423 448 473 373 398 423 448 473 373 398 423 473 373 398 423 448 473 373 398 423 448 473 373 398 423 448 473 373 398 423 448 473 Mmax (g/g) 0.0242 0.0242 0.0242 0.0242 0.0242 0.0240 0.0240 0.0240 0.0240 0.0223 0.0223 0.0223 0.0223 0.0223 0.0368 0.0368 0.0368 0.0368 0.0317 0.0317 0.0317 0.0317 0.0317 0.0456 0.0456 0.0456 0.0456 0.0456 0.0439 0.0400 0.0400 0.0400 0.0400 0.0509 0.0509 0.0509 0.0509 0.0509 KL (bar 1 ) 90.2 33.5 16.2 7.10 4.40 218 79.3 33.5 8.23 1300 460 132 55.2 24.2 172 49.4 18.5 4.07 1100 226 68.1 26.5 12.2 89.5 37.7 14.5 8.06 5.00 1310 449 146 53.3 36.2 1090 265 121 50.1 20.3

1135

n-heptane

FCC

48

n-octane

FCC

59

Toluene

FCC

55

cations in rare-earth-exchanged zeolite Y are located in the inaccessible sodalite cages of the structure (Park and Se , 2000), and these are therefore unable to interact with aromatic molecules that are adsorbed. The results reported in Table 1 conrm the previous report (Ruthven and Kaul, 1996) that heats of adsorption for aromatic molecules in rare-earth-exchanged zeolite Y are signicantly lower than in zeolite NaX. One feature of the equilibrium adsorption results is that the Langmuir constants and heats of adsorption are similar for the two catalysts studied despite the fact that the FCC catalyst contains matrix component as well as zeolite. The fact that the value of Mmax for the linear alkanes in REUSY is about double that observed in FCC catalyst is unsurprising given the BET surface areas are 377 and 183 m2 =g, respectively. The results suggest that the amount of alkane adsorbed at equilibrium in the matrix component of the FCC catalyst is very small compared to the amount present in the zeolite component. The di erence in Mmax value between the FCC catalyst and REUSY is smaller when p-xylene is the adsorbate; this may re ect some adsorption of aromatic species in the matrix component at the temperatures studied. 3.3. Measurement of rates of adsorption and desorption The TEOM results showing the transient adsorption and desorption curves for p-xylene in 64 mg of FCC catalyst at 373 K at four di erent helium owrates (50200 ml=min at STP conditions) are shown in Fig. 4. It can be seen that the curves are signicantly a ected by gas owrate, with mass changes taking place slower at lower owrates. The changes are su ciently slow that the dead volume in the apparatus cannot be the reason for the e ect. One possibility is that external mass transfer e ects may become signicant at slow owrates. However, calculations of mass transfer coe cients using established correlations for packed beds (McCabe et al., 1993) suggest that this is not the case under the conditions used. The other reason that mass changes can depend on gas owrate is when the length of the bed of catalyst is signicant. Even though the bed length in the TEOM is small (about 0:5 cm), this is signicant at slow owrates for cases when adsorption is strong as is the case at 373 K. Under these conditions, adsorbate will preferentially adsorb at the top of the bed during the early stages of the adsorption step, leaving the bottom of the bed relatively free from adsorbate. Similarly during the desorption step, stripping will take place preferentially from the top of the bed in the early stages. When bed length e ects are signicant, the hydrocarbon concentration down the whole bed needs to be modelled (Ruthven, 1984; Yang, 1997; Do, 1998) rather than just adsorption within a single sphere being considered. This means that TEOM mass proles should not be tted to the equations derived for isolated particles (Crank, 1975) unless independence on carrier gas owrate has been conrmed. Such equations are commonly used in the analysis

p-xylene

FCC

66

n-hexane

REUSY

43

n-octane

REUSY

56

p-xylene

REUSY

57

Lercher, 1997; Kotrel et al., 1999; Denayer et al., 1997). It can be seen that there is an increase in adsorption strength with chain length. The heats of adsorption for aromatic molecules in zeolite Y have been found to depend critically on the number and identity of available cations. For example, the heat of adsorption of p-xylene in zeolite NaX is 90 kJ mol1 , but only 64 kJ mol1 in zeolite LaY (Ruthven and Kaul, 1993, 1996). The reason for this is that aromatic molecules interact strongly with cations that are accessible to them; for example, this has been shown to be the case for zeolite NaY (Klein et al., 1994). However, many of the

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0.035

C.K. Lee et al. / Chemical Engineering Science 59 (2004) 1131 1138

0.035

mass adsorbed (g/g of catalyst)

mass adsorbed (g/g of catalyst)

0.03 0.025 0.02 0.015 0.01 0.005 0 -0.005 0 5 10 15 20 200 ml/min 150 ml/min 100 ml/min 50 ml/min

0.03 0.025 0.02 0.015 0.01 0.005 0 -0.005 0 50 100

373 K 398 K 423 K 448 K 473 K

150

(a)
0.035

time (s)

time (s)
Fig. 5. Mass measurements for a 60 s pulse of p-xylene (partial pressure 0:058 bar) on FCC catalyst at the temperatures indicated using a helium owrate of 200 ml=min (at STP conditions). For the sake of clarity, not all data points recorded by the TEOM are shown.

mass adsorbed (g/g of catalyst)

0.03 0.025 0.02 0.015

50 ml/min 100 ml/min 150 ml/min 200 ml/min

1.2

Normalised mass adsorbed

0.01 0.005 0 -0.005 0 50 100 150 200

1 0.8 0.6 0.4 0.2 0 0 50 100 150

373K: REUSY 373K: FCC 423K: REUSY 423K: FCC

(b)

time (s)

Fig. 4. (a) Adsorption and (b) desorption proles for p-xylene in 64 mg of FCC catalyst at 373 K. The helium owrate was varied and is given in the legend (values are those at STP conditions). The partial pressure of p-xylene was switched between 0 and 0:058 bar. The time t = 0 for each plot was chosen so that the change in mass starts at the same point on each graph. For the sake of clarity, not all data points recorded by the TEOM are shown.

200

250

time (s)
Fig. 6. Normalised mass measurements for a 60 s pulse of p-xylene (partial pressure 0:058 bar) on FCC catalyst and pure REUSY at 373 and 423 K using a helium owrate of 200 ml=min (at STP conditions). For the sake of clarity, not all data points recorded by the TEOM are shown.

of so-called zero length column (ZLC) experiments (Eic and Ruthven, 1988), though even with these it is important to check for bed length e ects (Brandani et al., 1996). For cases when there is less adsorption than the situation shown in Fig. 4, because of higher temperature, lower hydrocarbon partial pressure, or smaller quantity of catalyst, then the TEOM gives identical results at gas owrates of 150 and 200 ml=min. In these situations (and only these situations), the environment around each particle in the catalyst bed can be treated as the same and a model for the balance used that considers transport solely within a single catalyst particle. For this reason, the remaining experiments reported in this paper were all conducted using helium owrates of 200 ml=min. Fig. 5 shows TEOM results for the adsorption and desorption of p-xylene from FCC catalyst at ve di erent temperatures using the same hydrocarbon partial pressure in the carrier gas. At 473 K, the loading is dilute and corresponds to a position on the linear part of the adsorption isotherm. Under dilute conditions, it is expected that the rate of des-

orption and adsorption will be identical (Ruthven, 1984); this is observed to be the case here. At temperatures lower than 473 K in Fig. 5, the loading is non-dilute and corresponds to the non-linear part of the adsorption isotherm. Under non-dilute conditions, the rate of desorption is slower than the rate of adsorption (Ruthven, 1984) as is observed to be the case in Fig. 5. The di erence in desorption rate compared to the adsorption rate implies non-linearity of the adsorption isotherm and indicates either that the e ective di usion coe cient varies with concentration or that mass transport e ects at the particle boundary are signicant. Fig. 6 shows a comparison of the rates of adsorption and desorption of p-xylene on the FCC catalyst and on the pure zeolite Y sample at two di erent temperatures. The data have been normalised so that the equilibrium mass adsorbed has a value of unity. It can be seen that the adsorption and desorption rates for the pure zeolite Y sample are almost identical to the rates for the FCC catalyst sample, notwithstanding the presence of matrix material in the latter. The same

C.K. Lee et al. / Chemical Engineering Science 59 (2004) 1131 1138

1.2

1137

Normalised mass adsorbed

1 0.8 0.6 0.4 0.2 0 0 30 60 90

p-xylene n-octane n-hexane

netic behaviour of n-hexane, n-heptane, n-octane, toluene and p-xylene in rare-earth exchanged zeolite Y follow the expected trends. Interestingly, adsorption and desorption rates for the FCC catalyst are almost identical to those for pure zeolite Y. This means that mass transport in the matrix component of the FCC catalyst is rapid and not a limiting step in the adsorption process under the conditions employed in this study. Acknowledgements

120

time (s)
Fig. 7. Normalised mass measurements for a 60 s pulse of (i) p-xylene, (ii) n-octane, and (iii) n-hexane on pure REUSY at 423 K using a helium owrate of 200 ml=min (at STP conditions). The hydrocarbon partial pressure was chosen so that the fractional loading was similar in each case; the actual fractional loadings were 30%, 40% and 28% for the three hydrocarbons, respectively. For the sake of clarity, not all data points recorded by the TEOM are shown.

We thank BP Oil and the Department of Trade and Industry, UK, for nancial support of this work. We also thank Dr Graham Ketley and Dr Michael Hodges (BP Oil) for their help with this project. References
Alpay, E., Chadwick, D., Kershenbaum, L.S., Barrie, P.J., Sivadinarayana, C., Gladden, L.F., 2003. TEOM analysis of the equilibria and kinetics of n-hexane and n-heptane adsorption on FCC catalyst/silicalite. Chemical Engineering Science 58, 27772784. Bhatia, S., Beltramini, J., Do, D.D., 1989. Deactivation of zeolite catalysts. Catalysis ReviewsScience and Engineering 31, 431480. Brandani, A., Xu, Z., Ruthven, D., 1996. Transport di usion and self-di usion of benzene in NaX and CaX zeolite crystals studied by ZLC and tracer ZLC methods. Microporous Materials 7, 323331. Chen, N.Y., Degnan Jr., T.F., Smith, C.M., 1994. Molecular Transport and Reaction in Zeolites: Design and Application of Shape Selective Catalysts. VCH Publishers, New York. Chen, D., GrHnvold, A., Rebo, H.P., Moljord, K., Holmen, A., 1996a. Catalyst deactivation studied by conventional and oscillating microbalance reactors. Applied Catalysis A: General 137, L1L8. Chen, D., Rebo, H.P., Moljord, K., Holmen, A., 1996b. E ect of coke deposition on transport and adsorption in zeolites studied by a new microbalance reactor. Chemical Engineering Science 51, 26872692. Chen, D., Rebo, H.P., Moljord, K., Holmen, A., 1997. In uence of coke deposition on selectivity in zeolite catalysis. Industrial and Engineering Chemistry Research 36, 34733479. Chen, D., Moljord, K., Fuglerud, T., Holmen, A., 1999a. The e ect of crystal size of SAPO-34 on the selectivity and deactivation of the MTO reaction. Microporous and Mesoporous Materials 29, 191203. Chen, D., Rebo, H.P., Moljord, K., Holmen, A., 1999b. Methanol conversion to light olens over SAPO-34. Sorption, di usion, and catalytic reactions. Industrial and Engineering Chemistry Research 38, 42414249. Chen, D., Rebo, H.P., Holmen, A., 1999c. Di usion and deactivation during methanol conversion over SAPO-34: a percolation approach. Chemical Engineering Science 54, 34653473. Chen, D., Rebo, H.P., GrHnvold, A., Moljord, K., Holmen, A., 2000. Methanol conversion to light olens over SAPO-34: kinetic modeling of coke formation. Microporous and Mesoporous Materials 3536, 121135. Corma, A., 1993. Transformation of hydrocarbons on zeolite catalysts. Catalysis Letters 22, 3352. Corma, A., Orchill s, A.V., 2000. Current views on the mechanism of e catalytic cracking. Microporous and Mesoporous Materials 35, 2130. Crank, J., 1975. The Mathematics of Di usion. Clarendon Press, Oxford. Cumming, K.A., Wojciechowski, B.W., 1996. Hydrogen transfer, coke formation and catalyst decay and their role in the chain mechanism of catalytic cracking. Catalysis ReviewsScience and Engineering 38, 101157.

result was found with the other hydrocarbons studied in the temperature range studied (373473 K). It can therefore be concluded that the presence of matrix does not signicantly in uence the rate of uptake and desorption from FCC catalyst samples for the simple alkanes and aromatic molecules studied in this work, and thus that molecular transport in the matrix component is rapid. Fig. 7 shows a comparison of the rates of adsorption and desorption for p-xylene, n-octane and n-hexane in pure zeolite Y sample at 423 K. The kinetics will, in general, not only depend on temperature but also on the adsorbate loading, particularly if the loading becomes close to saturation. For this reason, the experimental data shown in Fig. 7 were obtained at fairly low hydrocarbon partial pressures so that the systems were far from saturation and had roughly similar fractional coverages. It can be seen that n-hexane adsorbs and desorbs far faster than n-octane which adsorbs and desorbs slightly faster than p-xylene. This is in the order expected based on the heats of adsorption determined in Table 1. More detailed analysis of the rates will be discussed in an accompanying paper. 4. Conclusions It has been demonstrated that it is possible to measure adsorption and desorption kinetics of hydrocarbons using a TEOM. It is important to minimise dead volumes and pressure imbalance e ects when studying fast adsorption processes. It is also important to perform experiments at di erent carrier gas owrates and/or using di erent amounts of catalyst in order to see whether these a ect the overall kinetics. The qualitative results presented in this paper show that the adsorption equilibrium and ki-

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