APPLIED CATALYSIS

A: GENERAL

ELSEVIER

Applied Catalysis

A: General

154 (1997) 221-240

Dealumination of HZSM-5 zeolites: Effect of steaming on acidity and aromatization activity

Antonio de Lucas*, P. Canizares, A. Durhn, A. Carrero
Department of Chemical Engineering, Faculty of Chemistry University of Castilla-La Mancha. Ciudad Real, Spain Received 22 July 1996; received in revised form 16 October 1996; accepted 16 October 1996

Abstract Conversion of acetone/n-butanol mixtures (1 : 2 wt/wt) to hydrocarbons over HZSM-5 zeolites previously dealuminated by (a) steaming and (b) steaming with subsequent HCl leaching has been studied at different conditions. Steamed-treated catalysts largely enhance their deactivation behavior. Al species are dislodged during the dealumination process, thereby reducing the strength and density of the acid sites of the parent catalyst. Catalysts dealuminated by means of steam-HCl treatment were found to have the best aromatization stability (the loss in residual aromatization activity decreases from 70% in the parent to only 12% in treated catalysts after 5 h of reaction). This treatment produces a decrease in both acid strength as measured by tert-butylamine temperature programmed desorption (from Td=280C to Td =230(Z) and acid density (from 0.23 to 0.13 mmol TBA g$). Medium/strong acid sites ratio close to unity and Brijnstednewis acid sites ratio lower than unity are characteristic in catalysts with the best deactivation behavior. Dealumination treatments generate a secondary pore structure that can contribute to enhance aromatization stability by reducing diffusional limitations.
Keywords: Steaming; HCl; Aromatization stability: HZSM-5; Acid sites

1. Introduction Since the introduction of ZSM-5 by Mobil Oil [I], extensive studies have been reported and this zeolite has gained increasing importance as a high-potential catalyst in a number of commercially important processes [2,3].

* Corresponding

author. E-mail: alucas@inqu-cr.uclm.es.

0926-860x/97/$17.00 0 1997 Elsevier Science B.V. All rights reserved PIZ SO926-860X(96)00367-5

222

A. de Lucas et aL /Applied Catalysis A: General 154 (1997) 221-240

ZSM-5 zeolite shows higher resistance to deactivation by coke deposition than other commercial zeolites types, which has been related to the absence of large cavities in the pore structure and to its low concentration of acid sites [4,5]. The formation of coke in hydrocarbons reactions over acid zeolite catalysts inhibit further reaction either by competitive removal of acid sites or by blocking access of reactant molecules to the acid sites. The number and nature of the acid sites clearly influences coke deposition and its effects. The control of the location of coke formation has some industrial interest. While it is unlikely that coke formation can be entirely eliminated in all reactions of interest, it appears possible to make some changes to improve the behavior. Thermal and hydrothermal pretreatments of zeolites are usually employed to modify their acidity and catalytic activity [6-9]. The influence of water vapor treatment at high temperatures on the properties of zeolite is particularly interesting while preparing catalysts for industrial applications with high activity, selectivity and stability. It is known that steaming leads to dealumination of the zeolite structure [ 10] and hence, to an increase in the stability of the sample. Lago et al. [11] reported the generation of catalytic sites with specific efficiency by mild steaming. Depending on the water vapor pressure, the treatment temperature and time, aluminium could be removed from the framework but not from the crystallite (so called nonframework aluminium or extralattice aluminium). Moreover, Kuehl [ 12] suggested that aluminium removed from the framework occupied cationic positions with an octahedral coordination and exhibited Lewis acid properties. By 27A1 n.m.r, spectroscopy two different states of nonframework have been detected [13,14]: octahedrally and tetrahedrally coordinated species. However, few attempts have been made in order to correlate the presence of nonframework aluminium with activity and stability of zeolites. In the conversion of alcohols or lower olefins [15,16] and n-butanol/acetone mixtures [ 17,18] to hydrocarbons, aromatic hydrocarbons may represent more than 25-30% of the total hydrocarbon yield with a high selectivity towards the formation of C7 and Cs aromatics. Both the catalytic activity and product selectivity in the above mentioned reactions are strongly affected by poisoning of stronger acid sites of the zeolite with coke. In a previous work [ 19], the one-step conversion of acetone/n-butanol mixtures (at compositions expected from fermentation processes) to hydrocarbons, mainly aromatics, using HZSM-5 based catalysts have been studied. A rapid catalyst deactivation was observed and aromatic hydrocarbons yield was strongly affected with time on stream. The aim of this paper is to improve catalysts deactivation behavior by modification of HZSM-5 by both steaming and steaming with subsequent HC1 leaching. The effect of these pretreatments on acidity and extent of aromatization reactions is also studied.

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

223

2. Experimental

2.1. Catalyst preparation

NaZSM-5 (Si/Al=45) was synthesized according to the method described elsewhere [20] using ethanol as template. X-ray diffraction as determined using a Cuot radiation and a nickel filter by means of a Philips PW/1700 diffractometer confirmed that the materials were ZSM-5 and presented 100% crystallinity. The parent catalyst (HZSM5-P) was obtained after binding and activating the NaZSM-5 according to Durfin [19]. NaZSM-5, as synthesized, was firstly bound with sodium montmorillonite (30% wt) to give the catalyst mechanical resistance. Then, it was calcinated at 550C for 5 h and exchanged with HC1 (0.6 N) at 25C. Finally the catalyst was activated at 550C for 14 h. This method was selected since the catalyst prepared in this way presented the best deactivation behavior.

2.2. Apparatus and procedure

Reactions were carried out in a plug continuous flow reactor consisting of a 36 cm stainless steel tube (1 inch diameter) surrounded by three heating zones, one of them acting as preheater. The temperatures of each zone were controlled independently within -4-1C by individual controllers. A cold trap (0C) down the reactor was used to collect water and gasoline-range products. The remaining products pass by the back-pressure regulator and were analyzed by an on-line chromatograph (Hewlett-Packard Series II) fitted with a Poraplot column attached to a thermic conductivity detector. The liquid product (collected in the cold trap) was periodically discharged and analyzed after separating the aqueous fraction by means of gas chromatography and using a PONA column connected to a flame ionic detector. Reaction was carried out using the following conditions: T =400C, W H S V - I = 0 . 5 h (gcat g~eeldh -1) and P = 1 atm. Under these conditions, conversion was always 100%. Steam-treated catalysts were prepared as follows: samples were placed in the reactor and heated up to the pretreatment temperature (450-500-550C) in a flow of N2. Water was added by means of a piston pump, keeping WHSV- ~ (h) in 0.30.8 during a treatment time of 4-12 h. Catalysts were quenched to room temperature and samples were taken in order to obtain characterization parameters before reaction. Nomenclature used in the catalysts is stated as HZSM5-Temperature-WHSV -1 (e.g. HZSM5-550-05 is a catalyst steamed at 550C and WHSV-1 of 0.5 h during the steaming pretreatment). The steam-HC1 treated zeolites were obtained using HZSM-5 steamed at 550C with WHSV-~=0.5 gcat gwater -1 h -1 for 4 h, followed by leaching in HC1 (0.6-1.2 N) at 80-100C for 12 h using 15 ml acid solution/gzeolite; finally samples were washed with water. Final catalysts were named from HZSM5(A 1) to HZSM5(A4) according to increasing order in the severity during the HC1 treatment.

224

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

2.3. Catalyst characterization

Dealuminated samples were characterized by X-ray powder diffraction in order to confirm the reservation of the crystallinity of the zeolite after treatments. Specific surface measurements were made using BET method. Total surface acidity was determined by adsorption and later desorption of tertbutylamine (TBA) in a Perkin-Elmer TGA-7 thermogravimetric analyzer according to reference [21]. The peak corresponding to the chemically desorbed TBA is related to the acid sites and is quantified in terms of mmol TBA]gcatalyst. The temperature at which this peak appears is related to the strength of the acid sites. Although t-butylamine may partially react to desorb as ammonia and alkene products at about 400C [22,23], it was completely desorbed at 300C under our experimental conditions. Desorption temperatures are strongly affected by experimental conditions and type of material (HZSM-5 bound with 35% wt of sodium montmorillonite in this study) [22]. An important information can be obtained about the acidity strength distribution of the zeolite by studying changes in the vibrations of pyridine previously adsorbed in the region of 1600 cm -1 to 1400 cm -1 [24]. Thus, infrared spectra at different saturation temperatures of pyridine were recorded using a Perkin Elmer 16 PC-FTIR. Prior to adsorption, the samples were pressed into thin wafers, evacuated under vacuum at 400C for 16 h, cooled to room temperature and saturated with pyridine. External surface acidity of catalysts was measured as the monolayer methylene blue (MB) adsorption capacity [25]. Three stock solutions of methylene blue (concentration range 2.76 10-41.23 10 -3 mol dm -3) were prepared by weight. Samples of the zeolite (ca. 100 mg) were equilibrated with aqueous solutions of the dye for 24 h at room temperature. The supernatant solution was diluted and its absorbance at 664 nm was recorded by a spectrophotometer (Perkin Elmer Lambda 3B). Monolayer adsorption was estimated from Langmuir isotherm plot. A1 content of catalysts was determined by means of a Thermo Jarrel Ash Atomic Absorption Spectrophotometry at 309.3 nm and using a N20-CzH2 flame. The coke content was determined by combustion in a thermogravimetric analyzer using a stream of 20 cm 3 of oxygen and increasing temperature from 150 to 700C at 10C min -1. The weight loss between 350 and 700C was attributed to coke.

3. Results and discussion

3.1. Reaction with the parent catalyst, HZSM5-P

Reaction was carried out using the following conditions: T=400C, W H S V - I = 0 . 5 h (gcat greed -1 h -1 ) and P= 1 atm. Under these conditions, conversion was always 100%, but product distribution suffered important changes with time

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

225

Table 1 Hydrocarbons distribution in the catalytic conversion of n-butanol/acetone mixtures on HZSM5-P. (T=400' C; WHSV-~=0.5 h; P = I atm; Conversion=100%) Time on stream (h) Hydrocarbons (% wt) Methane
Ethane Propane 0.5 0.1 0.6 15.1 11.6 8.5 35.9 1.5 0.1 0.5 15.7 11.5 7.5 35.3 2.5 0.3 12.1 10.4 7.3 30.2 3.5 9.6 8.4 7.1 24.9 4.5 6.7 6.1 6.6 19.5

/-Butane n-Butane Total paraffins

Ethylene
Propylene

1-Butene t-2-Butene c-2-Butene Total olefins

1.3 3.8 3.6 0.3 0.2 9.2

1.3 3.7 3.7 0.5 0.4 9.6

1.9 5.1 5.0 1.4 1.2 14.6

2.3 6.7 6.9 1.6 1.5 19.0

2.1 9.8 9,5 2,3 2,2 26.1

C~ paraffins C5 olefins C6-C 9 non-aromatic C5-C9 non-aromatic

7.0 0.7 5.6 13.3

6.5 3.6 9.8 19.9

6.3 5.6 14.7 26.6

4.5 7.3 21.9 33.7

3.7 10.1 25.1 38.9

Benzene Toluene Ethylbenzene m-p-xylenes o-xylenes n-propylbenzene Trimethylbenzenes

Clo + aromatics
C6-C1 o aromatic

2.8 14.8 2.0 13.3 1.2 0.3 5.0 2.2 41.6

1.0 9.1 2.0 12.9 0.7 0.2 5.9 3.4 35.2

0.5 5.4 1.5 11.4 0.6 0.3 6.1 2.8 28.6

0.2 3.3 0.7 8.8 0.4 0.2 5.0 3.8 22.4

0.2 2.0 0.5 5.6 0.4 0.2 3.8 2.8 15.5

on stream; aromatic hydrocarbons and gaseous paraffins decreased, whereas olefins and liquid paraffins increased as a consequence of catalyst deactivation by coking. Detailed evolution of hydrocarbons distribution is summarized in Table 1. The aromatization activity of the catalyst is strongly affected by the decrease in the number of active sites available with time on stream. However, even when many acid sites are blocked (after 5 h) the n-butanol/acetone mixtures are completely converted into hydrocarbons, suggesting that the primary reactions involved in the conversion of the mixture to lower hydrocarbons occur on weaker sites, while the dehydrocyclization reactions leading to the formation of aromatic requires strong acid sites, which is consistent with earlier observations [16].

226

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

AROMATIC HYDROCARBONS DISTRIBUTION (%wt)

50
X

X x

40 30 20 10
0

-"

dr

--

TIME ON STREAM (h)

Fig. 1. Aromatic hydrocarbons distribution in HZSM5-P during the conversion of n-butanol/acetone mixtures to hydrocarbons. (Reaction conditions: T=400C, WHSV l =0.5 h, P = I atm). (o benzene; O toluene; C8 AR; C9 AR; ~ Clo AR).

The distribution of aromatic produced in the reaction show a decrease in the concentration of benzene and toluene and an increase in that of higher aromatics with time on stream, due to the availability of strong sites (Fig. 1). This is expected to be due to the dealkylation of the higher aromatics on stronger sites. In this work, the aromatic hydrocarbons fraction will be considered as a reference to study the deactivation of catalysts, since they are the main fraction in the liquid hydrocarbon product and are important precursors of coke.

3.2. Dealumination by steam treatment 3.2.1. Influence of temperature and W H S V -1 (gcat gwater -1 h - 1 ) Several catalysts were first prepared by steaming the parent catalyst at different conditions of temperature and WHSV -1 during the pretreatment (details in Table 2). Initial aromatic hydrocarbons yield (defined as aromatic hydrocarbons yield (%wt) at time on stream=0.5 h) versus steaming temperature is shown in Fig. 2, for catalysts steamed at different WHSV -~ ratios. A decrease in initial aromatization activity can be observed when there is an increase in temperature during the steaming pretreatment. This is due to the presence of significant amounts of A1 atoms in the zeolite surface as a consequence of the migration of reticular A1 in the tetrahedral positions to extemal zones of the zeolitic structure, therefore occupying cationic positions. In other words, A1 atoms in a tetrahedral position are displaced to an octahedral one, [26], destroying

A. de Lucas et a l . / A p p l i e d Catalysis A: General 154 (1997) 221-240

227

tm.
I I I

[..,
t",l ~ I I ~ I I I

r..)

<

~2
b-,
~Z

-=U
et",l

e.

"r"

g
?
e.

Z~

i?
e~

e~

N N

228

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

35 30
25

INITIALAR YIELD (%wt)

20

15 10

X HZSM5-P ] [] WHSV~=0.3 ] WHSVI=0'5 I O WHSVI=0.8 I

/,'

I 450

I 500 TEMPERATURE (C)

550

Fig. 2. Initial aromatic hydrocarbons yield in steamed catalysts during the conversion of n-butanol/acetone mixtures to hydrocarbons, (Reaction conditions: T=400C, WHSV 1=0.5 h, P=I atm).

synergism between framework hydroxyls and aluminium atoms, thus leading to a decrease in catalytic activity [27]. In order to compare the aromatization stability of the parent catalyst and those steamed at different conditions (temperature: 450-550C, WHSV-I: 0.3-0.8 h) and because of the variation in initial aromatization activity, a new variable has been stated as Residual Aromatization Activity, aar, (defined as aromatic hydrocarbons yield at a certain time on stream/initial aromatic hydrocarbons yield). Evolution of aar is shown in Fig. 3 for catalysts dealuminated at different WHSV-1 ratio and temperature. Two facts should be noticed: 1. When a relatively great amount of water is used during the pretreatment (low WHSV -1, Fig. 3a), a better stability is achieved at low steaming temperatures (450C). An increase of this parameter deteriorate the catalysts stability, although all of them deactivate slower than parent catalyst. 2. When intermediate and high WHSV -Z ratio and low amount of water are used, (Fig. 3 b and c) an increase of steaming temperature produces a sensitive improvement in catalysts deactivation behavior. The best results were obtained with catalysts steamed at 550C and WHSV -1 of 0.5 and 0.8 h. Catalyst with the best aromatization stability, steamed at 550C and WHSV-1 of 0.5 h, shows a loss of aromatic hydrocarbons yield of about 30% after 5 h compared to a 70% aromatic hydrocarbons loss found in the parent catalyst under the experimental conditions used during this investigation (T--400C, WHSV-I=0.5 h; P = I atm).

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240 ant

1 0.8 0.6 0.4 0.2 0 0 1 2 TIME (h) 3 4 HZ'SM5-500..03 I i HZSM5-550-03 ~

229

aar
1 0.8 0.6 0.4 0.2 0

(hHZSM5-500-05
0 HZSM5-550-05 I 1 0 TIME (h) I 3

I 4

aar
1 0.8 0.6 0.4 X HZSM5-P 0.2 o 0 1 2 3 4 5 (h HZSM5-500-08 HZSM5-550-08 C

TIME [h)

Fig. 3. a~r vs. time on stream in catalysts dealuminated by steaming treatment at different conditions: (a) W H S V - I = 0 . 3 h, (b) WHSV -1 =0.5 h, (c) WHSV 1=0.8 h.

In order to explain these results, the parent and steamed catalysts were characterized. Firstly, A1 content was determined as described above. Results are summarized in Table 2. No change in A1 content was found, since steaming under studied conditions leads to dealumination of the zeolite surface with the formation of dislodged aluminium which remains in the zeolitic channel as

230

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

0.00 -0.05 -0.10 E E -0.15

0~ v

-o.2o
-0.25 -0.30 -0.35 ....
. . . . . .

(.9
t~ HZSM5-450-05 ~,,'i HZSM5-550-05 ~J ~,~

1~0

'

1~0

' 2~0

' 2'~0

'

3~0

3;0

400

TEMPERATURE (* C)
Fig. 4. DTG curves corresponding to desorption of TBA in HZSM5-P and HZSM5-550-4)5.

cationic species [7,8]. This structural change does not affect crystalline structure, as confirmed by X-ray diffraction (Table 2). Table 2 also reports total surface acidity and TBA desorption temperature in steamed catalysts. Common tendencies are to link the desorption temperatures to the strength of the acid sites. Since desorption features (area and position of desorption peaks) observed with HZSM5-P and steamed-ZSM-5 are quite different (Fig. 4), it is reasonable to say that steaming, under these conditions, significantly affects acid properties. Acid strength of the parent catalyst decreases (from Td=280C to To=210C) whereas density of the acid sites follows the same trend (from 0.23 to 0.11 mmol TBA g~alt) when steaming conditions (Tand/or WHSV -1) are more and more severe. This fact explains the lesser initial aromatic hydrocarbons yield obtained with the steamed catalysts as previously commented in Fig. 2. Moreover, the aromatization stability will be enhanced in those type of catalysts since the new active sites appearing at Td=210C are weaker and contribute to a lesser extent to coke formation [19].
2.3: 2.2 2.1 2.0 3
1.9 1.8

==
E

1.7 1.6 1.5 1.4 1.3 1.2 I 1400 , = 1450

I 1500 cm
, i , i

1550

1600

-1

Fig. 5. IR spectra corresponding to pyridine desorption at Td=400C in steamed catalysts.

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

231

In addition, the adsorption of pyridine as a well known indicator for acidic sites, was investigated by infrared spectroscopy. An infrared spectra corresponding to pyridine desorption at 400C of steamed catalysts is shown in Fig. 5. The band at 1540 cm -1 attributed to pyridinium cation and due to pyridine adsorbed on Br6nsted sites is higher in the parent sample but decreases when steaming at higher temperatures. Otherwise, the band at 1450 cm-1 due to pyridine adsorbed on Lewis sites increases with steaming temperature. This fact can be explained since dealumination reaction requiring the partial rearrangement of the aluminosilicate framework may be formulated as follows [28]:

O-

\ ~0+ ~ o
*"

OH AIO + ~si/OH

\ /0

. ~ s i _ _ o / A Io / S / ~

o \ si //\

/ \ =,/ o/S~../\

The positive charge sited on the extra framework A10 + species will be partially neutralized by electron donation from the hydroxyls oxygens and from oxygens of water molecules; a decrease in the number of Br6nsted acid sites and an increase in Lewis sites corresponding to A10 + species will follow as confirmed in our steamed catalysts. In order to compare the acid strength distribution in steamed catalysts, the decrease of the intensity of Br0nsted and Lewis bands (AL arbitrary units) with the pyridine desorption temperature calculated at different temperature intervals (1500 200, 200-400, >400C) is shown in Fig. 6. Weak sites are considered to be related with the desorption between 150 and 200C, that is 12oo-115o; medium strength sites are those desorbed between 200 and 400C and strong sites those with Td >400C.The following points can be considered: The parent catalyst shows a concentration of strong acid sites (Ta >400C) much higher than weak and medium sites (Td=1500200 and 200-400C respectively), thereby showing the density of Br6nsted sites higher than that of Lewis sites. On the contrary, in HZSM5-550-05 (selected as the catalyst with the best aromatization stability), strong sites/medium sites ratio is very close to l, Lewis sites always in higher concentration. When dealumination conditions are severe (HZSM5-550-03), an increase in the number of weak sites and a decrease in strong and medium sites is observed. However, in mild conditions (HZSM5-450-03) the proportion of medium and strong sites increases, showing the number of strong Br6nsted sites higher than the strong Lewis sites, similar situation to that previously found in the parent catalyst.

232

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

. '8 & I(a.u.)

1.6 Al(a.u.) 1.4 1.2

1 0.8

0.6

0.4

0.6 0.4 0.2 0 0.2

150-200 200-400 >400 Desorption temperature (~C)

8)

150-200

200-400

LI
> 400

Desorption temperature (13)

b)
0.8 Al(a.u.)

0.8

&l(a.u,)

0.6

0.6

0.4

0.2

0: A/J
150-200 200-400 >400 Desorption temperature ('C) 150-200 200-400 > 400 Desorption temperature (C)

0.4

c)

d)

Fig. 6. Acid strength distribution in (a) HZSM5-P, (b) HZSM5-5504)5, (c) HZSM5-550-03 and (d) HZSM5450-03. (D Lewis sites Br6nsted sites)

The high density of weak sites in all the steamed catalysts would explain the lower initial aromatic hydrocarbons yield found when used in reaction, since aromatization reactions require the presence of strong sites [29]. On the other hand, the weaker strength of active sites in steamed catalysts compared to the parent catalyst should imply a decrease of the selectivities towards

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

233

0.8

0.6 0.4

>( HZSM5-P NaZSM5-550-05 HZSM5-550-05 C- HZSM5-(1.2)-550-05

~-

0.2 0

I
1

I
2 TIME (h)

Fig. 7. Influence of initial acidity of the parent catalyst on a~ evolution.

light aromatic hydrocarbons (benzene + toluene) in the first hour of reaction, which are formed throughout dehydrocyclization and dealkylation reactions that take place on strong sites. Effectively, a decrease in this parameter (from 42.3% in HZSM5-P to 34.4% in HZSM-550-05) is observed. To sum it up, it can be concluded that steamed catalysts with a better aromatization stability present a considerable lower acidity than parent catalyst (0.13 against 0.23 mmol TBA g-1 respectively) and a medium/strong sites ratio close to 1, with the number of Lewis sites higher than that of Brtnsted ones.

3.2.2. Influence of initial acidity of the parent catalyst

In order to study the influence of this parameter, two additional catalysts were prepared. One of them consisted of a zeolite ZSM-5 in its sodium form steamed in the above selected conditions (T-550C, t=4 h, WHSV-1--0.5 h) and lately bound and exchanged with HC1 0.6 N as described above. In the second case, the catalyst in its acid form was dealuminated, although the concentration of HCI used in the ion-exchange step was increased to 1.2 N. In Fig. 7, a~ versus time on stream for the two catalysts selected above, the parent and HZSM5-550-05, is shown. It can be noted that the catalyst dealuminated in its sodium form has the same behavior than the parent catalyst. Indeed, hydrolytic removal of A1 atoms is only possible from decationized lattice sites which are formed by zeolite ion-exchange with HCI: H

-Si ..... 0 ..... Al-O-Si-

234

A. de Lucas et aL /Applied Catalysis A: General 154 (1997) 221-240

and not from Na + containing sites of the type: I Na I I -Si .....O.....AI'-O-SiI I I It can be assumed that weakening of the A10 bond strength through polarization by the proton facilitates A10 bond splitting in the H-form of the zeolites. Total acidity and acid strength (Ta) remains unchanged when dealumination is made on the sodium zeolite (Table 2), confirming the above observations. Furthermore, no dislodgement of framework aluminium is achieved during steaming under these conditions. Moreover, an increase in the concentration of HC1 from 0.6 N to 1.2 N does not produce an improvement in catalysts deactivation behavior, but a decrease in initial aromatic hydrocarbons yield (from 28.4 to 20.3% wt), probably due to a partial loss of crystallinity as detected by X-ray diffraction (Table 2).

3.2.3. Influence of steaming time

In order to study the effect of the steaming time on catalyst deactivation, two additional catalysts were prepared by dealumination under mild conditions (T-450C; WHSV-1--0.5 h) and increasing the dealumination time from 4 to 12 h (Table 2). Influence of steaming time on aromatic hydrocarbons yield evolution is shown in Fig. 8. This parameter has no significant effect on aromatization stability in the studied range. When the steaming time increases to 8 and 12 h, the catalyst deactivation behavior is only slightly better. Although steaming time does not produce any sensitive change in acid strength, a progressive decrease in the number of acid sites is remarkable as steaming time
a ar

0.8 0.6 0.4 HZSM5-450-05-4 0.2 [] HZSMS-450-05-8

!

]
2
TIME (h)

.....

HZSMS-450-O5-12J

O 0 1

~ 3 4

Fig. 8. Influenceof steamingtimeon aa~evolution.

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

235

e~

oo

t~

"6 t ,.d i i

t'q

c~l

7 <

t'q

t'q

zZ
0 .= N C

U z g
o C

6
7 >

~
~

o
c
o

P
e ~

(.) c

236

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

INITIALAR YIELD (%wt)

30

25

20

"15

10

HZSM5-P HZSM5(A1) HZSM5(A2) HZSM5(A3) HZSM5(A4

a)
aar

0.8

0.6

0.4 ~HZSM5-P ~,HZSMS(A1) A HZSMS(A2) ~..IZS M5(A3) JHZSM5(A4)

0.2

0
0

I
1

I
2

I
3

I
4

TIME (h)

b)
Fig. 9. (a) Initial aromatic hydrocarbons yield in steamed-HC1 treated catalysts. (b) Influence of treating conditions on aromatization residual activity in steamed-HCl treated catalysts.

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

237

increases (Table 2). Nevertheless, this change is not very important in the studied range of times of pretreatment and leads to similar stability in all the catalysts. It was concluded that steaming temperature is the most important variable to be considered. The increasing effect of dealumination with rising temperature was also observed by Lutz et al. (1994) when studying the stability of high-silica Y-type zeolites [30].
3.3. Dealumination with steam-HCl treatment

In this section, the parent catalyst was firstly dealuminated by steaming under selected conditions (T--550C; W H S V - I = 0 . 5 h), together with a subsequent extraction with HC1 solutions (Table 3). Initial aromatic hydrocarbons yield (Fig. 9a) remains constant for all the catalysts tested in this section. Moreover, this treatment does not produce any change in the catalytic activity of dealuminated catalysts compared with the parent catalyst. Residual aromatization activity (Fig. 9b) show that this group of catalysts presents a largely enhanced aromatization stability. In this case, the loss of initial aromatic hydrocarbons yield is around 12% (in HZSM5(A2)) whereas steamed catalyst in the best conditions (HZSM5-550-05) and parent catalyst present a loss of 30% and 70%, respectively, after 5 h on stream. Regarding zeolite structure, aluminium loss induced in this group of catalysts (Table 3) never exceeded 20% and no significant destruction of the lattice was observed during dealumination under these conditions. Table 3 reports total surface acidity and TBA desorption temperature. SteamHC1 treatment causes a decrease in the number (from 0.23 to 0.13 mmolTBA g~-alt) and strength of acid sites (from Td=280 to 230C), Fig. 10a. Nevertheless, the new acid sites appearing at 230C have enough strength so that aromatization reactions can take place over them. The lesser number of strong sites confirms the decrease in coke formation and therefore a best deactivation behavior is seen when compared with the parent catalyst. Acid strength distribution in HZSM5-P and HZSM5(A2) is depicted in Fig. 10b. Dealumination catalysts present a larger number of Lewis sites than that of Brrnsted sites in all the temperature intervals. This fact also happened when the parent catalyst was dealuminated by steaming under the best conditions. In contrast to steamed catalysts, medium and strong Lewis sites are predominant in HZSM5(A2), where the ratio of medium/strong sites is very close to unity, and weak sites are lower in number. Thus, selectivities to ligth aromatic hydrocarbons in the first hour of reaction (47.7% in HZSM5(A2)) are in the same order of magnitude than those obtained with HZSM5-P (42.3%). Moreover, steaming produces an enrichment of A1 at the external surface (from 3.9 to 4.6 mmol MB gc~., that is an increase from 16.9% to 35.4% of total acidity), but acid leaching removes part of these aluminium species preferentially at the external surface (1.6 mmol MB g-1 in HZSM5(A2), 12.3% of total acidity).

238

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240

0.0

-o.1 z -0.2 l.o -0.3

. . . . HZSM5 (A2)
-0.4

~o

~o

~o
TEMPERATURE

~o
('C)

3~o

400

a)
Al(a.u.) zxI(a.u.)

1.6

0.8

1.2

0.4

150-200 200-400 > 400 Desorption temperature (*C)

I i
b)

0.6

0.2

b
150-200

200-400

Desorption temperature ( * C )

li
ii)

> 400

Fig. 10. (a) DTG curves corresponding to desorption of TBA in HZSM5-P and HZSM5 (A2). (b) Acid strength distribution in (i) HZSM5-P, (ii) HZSM5 (A2). ([] Lewis sites, Br6nsted sites).

In addition, specific surface, mesopore area and coke deposited after 5 h in HZSM5-550-05, HZSM5(A2) and HZSM5-P catalysts are reported in Table 4. After dealumination by steaming and steam-HC1 treatment, the mesopore area increases. This fact is explained since a secondary pore structure (over 2 nm diameter) can be produced as a consequence of aluminum extraction in dealuminated zeolites [31]. The formation of this new structure could act positively in catalysts deactivation behavior, as it can reduce diffusional limitations in the zeolitic channel.

A. de Lucas et al./Applied Catalysis A: General 154 (1997) 221-240 Table 4 Specific surface, micropore volume, mesopore surface and coke deposited in selected catalysts Catalyst HZSM5-P HZSM5-550-05 HZSM5 (A2) SBET (m 2 g l) 29 l 295 289 Vmp (cm 3 g-i) 0.14 0.12 0.16 AMp (m 2 g--l) 29.7 61.3 54.0

239

Coke (wt.-%) 6.57 3.30 5.20

Finally, HZSM5(A2) has the best deactivation behavior, even though coke content is lower in HZSM5-550-05. As it is widely known, catalysts deactivation is related with coke deposition mechanism, which not only depends on how much coke is deposited but also on the nature and location of that coke. Probably, coke on HZSM5-550--05 is more toxic due to higher external deposition (higher density of external sites) leading to blocking of zeolitic channels. Extensive studies about different coke deposition mechanisms over dealuminated HZSM-5 zeolites will be the object of future paper.

4. Conclusions
Deactivation behavior of steamed catalysts was found to be better under carefully controlled conditions depending on the interplay of several variables such as temperature, WHSV -1, steaming period and initial acidity of parent catalyst. Steaming treatment produces a decrease in acid sites strength and density, which is related to coke formation. Infrared data show an increase in weak and Lewis acid sites. Furthermore, medium/strong acid sites ratio is close to unity for catalyst with the best deactivation behavior. Steam-HC1 treatment also produces a decrease in the acid strength and density, leading to a similar acid strength distribution than steamed catalysts. The best deactivation behavior found in these catalysts must be explained in terms of toxicity of coke, which is dependent on coke content, location and nature.

Acknowledgements
Financial support from DGICYT (Direcci6n General de Investigaci6n Cient/fica y T6cnica, Project PB89-0494, Ministry of Education, Spain) is gratefully acknowledged.

References
[1] R.J. Argauer and G.R. Landolt, U.S. Patent 3702886, 1972. [2] N.Y. Chen and W.E. Garwood, Catal. Rev. Sci. Eng., 28 (1986) 185.

240 [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31]

A. de Lucas et aL/Applied Catalysis A: General 154 (1997) 221-240

ER. Pujad6, J.A. Rab6, G.J. Ant6s and S.A. Gembicki, Catal. Today, 13 (1992) 13. M. Guisnet and E Magnoux, Appl. Catal, 54 (1989) 1. D.M. Bibby, R.E Howe and G.M. McLlelan, Appl. Catal., 93 (1992) 1. G. Engelhardt and P. Lohse, Zeolites, 3 (1983) 233. Y. Sendoda and Y. Ono, Zeolites, 8 (1988) 101. R. Le Van Mao, T.M. Nguyen and J. Yao, Appl. Catal., 61 (1990) 161. E.V. Sobrinho, D. Cardoso, E. Fababella and J.G. Silva, Appl. Catal. A, 127 (1995) 157. J. Scherzer, Am. Chem. Soc. Syrup. Series, 247 (1984) 157. R.M.Lago, W.O. Haag, R.J. Mikovsky, D.H. Olson, S.H. Hellring, K.D. Schmidt and G.T.Herr, in Proceedings of the 7th Intenational Zeolite Conference, Tokyo 1986. Elsevier, Amsterdam, 1986, p. 677. G.H. Kuehl, J. Phys. Chem. Solids, 38 (1977) 1259. D. Freude, E. Brunner, H. Pfeifer, D. Prager, H.G. Jerschkewitz, U. Lohse and G. Oehlmann, Chem. Phys. Lett., 139 (1987) 325. A. Samoson, E. Lippmaa, G. Engelhardt, U. Lohse and H.G. Jerschkewitz, Chem. Phys. Lett., 134 (1987) 589. E. Costa, M.A. Uguina, J. Aguado and P. Hernandez, Ind Eng. Chem. Res., 24 (1985) 239. V.S. Nayak and V.R. Choudhary, Appl. Catal., 9 (1984) 251. E. Costa, J. Aguado, G. Ovejero and E Canizares, Ind. Eng. Chem., 31 (1992) 1021. O.A. Anunziata, O.A. Orio, E.R. Herrero, A.F. L6pez, C.E P6rez and A.R. Sufirez, Appl. Catal., 15 (1985) 239. A. Dur~in, Conversion of acetone/n-butanol mixtures to hydrocarbons over HZSM-5, Ph.D. Dissertation, University of Castilla-La Mancha, Spain, 1995. M.A. Uguina, A. de Lucas, E Ruiz and D.E Serrano, Ind. Eng. Chem. Res., 34 (1995) 451. A.G. Aguayo, J.M. Arandes, M. Ohizar and J. Bilbao, Ind. Eng. Chem. Res., 29 (1990) 1621. D.J. Parrillo, A.T. Adamo, G.T. Kokotailo and R.J. Gorte, Appl. Catal., 67 (1990) 107. A.K. Ghosh and G. Curthoys, J. Phys. Chem., 88 (1984) 1130. N.Y. T6psoe, K. Pedersen and E.G. Derouane, J. Catal., 70 (1981) 41. J.R. Anderson, Y.E Chang and A.E. Hugher, Catal. Lett., 2 (1989) 279. J. Dwyer, ER. Fitch, G. Quin and J.C. Vickerman, J. Phys Chem., 86 (1982) 4574. A.G. Ashton, S. Batmaniam, J. Bwyer, I.S. Elliot and ER. Fitch, J. Mol. Catal., 34 (1986) 73. EN. Aukett, S. Cartlidge and I.J.E Poplett, Zeolites, 6 (1986) 169. E Hudec, J. Novansky, S. SilhSx, N.T. Trung, M. Zubek and J. Madar, Adv. Sci. Tech., 3 (1986) 159. W. Lutz, B. Zibronius and E. L6effier, Stud. Surf. Sci. Catal., 84 (1994) 1005. H.K. Beyer, G. Borb~ly-Pfiln~ and J. Wu, Stud. Surf. Sci. Catal., 84 (1994) 993.