applied catalysis A

Applied Catalysis A: General 110 ( 1994) 3948

Dimerization of 1-butene over nickel zeolitic catalysts: A search for linear dimers
Paolo Beltrame,
Dipartimento

Lucia Fork, Antonello Talamini, Giovanni Zuretti

ed Elettrochimica, Univemird di Milano, Via Golgi 19, I-20133 Milan, Italy

di ChimicajGica

(Received

30 July 1993, revised manuscript

received 20 December

1993)

Abstract
Catalysts based both on nickel and ZSM-5 zeolites have been prepared and used for the dimerization of 1-butene. The reaction was performed at 40 and 80 bar and 100 to 200C in a fixed-bed flow reactor with gas-chromatographic (CC) determination of alkenes product fractions characterized by their C atom number. Hydrogenation and GC analysis of the alkane Cs isomers allowed determination of the degree of branching and of the linear isomers content of the CR fraction. The reactions detected were isomerization of 1-butene to 2-butenes, dimerization and further oligomerization of butenes. Favoured Cs products were in every case several dimethylhexenes; however, under appropriate conditions, considerable fractions of linear octenes were obtained. Key wordst dodecenes; isomerization;

Ni-ZSM-5 catalysts; octenes

1. Introduction
Dimerization of lower alkenes is a well known upgrading process, leading to more useful alkenes, from which alcohols and other products can be obtained. Within the dimer fractions,

linear alkenes are of special interest and their formation has been pursued with particular attention. Even considering only heterogeneous catalysis and C,-C4 alkenes, a series of reports on this subject can be mentioned [ l-201, where fractions of linear dimers as low as 3% and as high as 65% are reported. Most of the catalysts used are based on nickel or (less often) cobalt, although purely acidic catalysts have been employed at times. Considering that the aim of obtaining linear rather than branched alkenes can be related to the subject of shape selectivity, it is surprising that only a few attempts at using zeolites of the ZSM-5 type have been reported [ 11,131. Both these papers refer to propene as the alkene; fractions of linear dimers around 30% are reported, although it is not clear whether acidic
*Corresponding author. Fax. ( + 39-2) 70638129

0926-860X/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved .SSDIO926-860X (93)E0263-C

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Table 1 Main characteristics Catalyst A

of the catalysts employed AS B HNaNi-ZSM-5 79.7 Silylated with HMDS; I.1 wt.-% SiO, added None C NiO-Alz03/SiOzL 23.1 None D Co/P

Type
SiOZ/A120a molar ratio Treatment

HNaNi-ZSM-5 17.5 None

_
Impregnated withaq.(25 wt.-%)soln.of NH,

&&ace acidity (meq/g) 0.032 0.148 IprY,< -3.71 0.206 0.999 [P&G 1.51 Flowing air up to 500C Activation conditions

0.053 0.347

0.03 1 Flowing Nz at 450C

0.033

0.81 wt.-% Ni; formula: H,,2Na,.,Ni,~,x(A10,)9,~(SiO~)~~.~. 0.45 wt.-% Ni; formula: (H,Na) ,.45Ni0.45(AlO>) z 35( SiOz)s-c.os. 2.8 wt.-% Ni + A1?O1 on amorphous silica; 10.2 wt.-% Co on BDH charcoal Lot no.1527630.

zeolites are sufficient to reach this goal [ I I] or exchange with nickel is required [ 131. It seemed appropriate to investigate the dimerization of butenes, on catalysts associating the properties of ZSM-5 zeolites and of nickel. This was the aim of the present work, for which catalysts A, AS and B (Table 1) were prepared, A from a high alumina ZSM-5, AS by silylating A with hexamethyldisilazane (HMDS) and B from a low alumina ZSM-5. In particular, the silylation of A to AS was performed hoping to block only external acid sites and force the dimerization to take place within the pores, possibly with shapeselectivity effects. For the sake of comparison, two well proven catalysts have been prepared (C and D in Table 1), that is NiO-A120, on amorphous silica [ 68,191 and Co0 on carbon [ 2,3]. Reactions were carried out under pressure (40 or 80 bar), at different temperatures in the range 100_200C, by feeding pure 1-butene.

2. Experimental 2. I. Reactant and catalysts I-Butene was a commercial product 99 + which has been checked by our analytical method to be 299.9% pure. Zeolites of the ZSM-5 type were prepared according to the usual procedure [ 211. Catalyst A was obtained by exchange of a high alumina zeolite with ammonium and then nickel acetates: atomic absorption (AA) analysis (for nickel and sodium) gave mainly Na cations, 17% substituted by Ni, 12% by H. Catalyst AS was silylated as described by Wilshier et al. [ 111, under nitrogen 99.999 + instead of argon. Catalyst B was obtained from a low alumina zeolite, by exchange with ammonium acetate and then nickel nitrate: nickel cations were determined by AA analysis, but the amount of sodium was too small to be evaluated precisely. All catalysts were used after being pressed in wafers (2 tons/cm2), crushed and sieved to 0.18-0.36 mm (40-80 mesh)

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41

particle size. Surface acidity was measured by titration with n-butylamine in an anhydrous solvent [ 221, using proper indicators. Details about the catalysts employed are summarised in Table 1. 2.2. Apparatus and procedure Reactions were carried out in a stainless steel (AISI 316) continuous flow reactor (6 mm I.D.; 250 mm length), having an axial thermowell, so that the available volume was 5.3 cm3. The reactor was fed by an ISCO pLC-500 micro flow pump (feed rate [Fl in the range 0.009-0.032 mol/h) through a preheater. Both preheater and reactor were kept in an electric furnace, with temperature controlled to k 1C. Only a small central portion of the reactor was actually containing the catalyst (usual mass [WI 0.5 g and never more than 1 g) : the rest of the volume was filled with inert quartz powder of the same particle size. Zeolitic catalysts were activated in flowing air at temperatures from 250 to 500C. When required, they were regenerated in flowing air at 500C. Catalysts C and D were activated in flowing nitrogen at 450C. The reactor effluent passed through a condensing trap, kept at room temperature, from which gases went through the sampling valve of an in-line gas chromatograph followed by a volumetric gas meter, while liquids were collected (usually for 1 h), weighed and later subjected to the same analysis. This was done on a PONA capillary column (50 m long, 0.2 mm I.D., 0.5 pm film), operated at temperatures from 10 to 200C. A few peaks were identified by comparison with pure samples (isobutane, lbutene, n-butane, 2-butenes) ; other peaks were classified, according to the mass of the corresponding components, by gas chromatography-mass spectrometry (CC-MS) determinations, as C,, Cg, C ,,.. ., C,*, C,,, C,,, alkenes; these fractions had well defined ranges of retention time values. By comparison with a pure sample of isobutene, it was ascertained that this compound had a retention time almost identical to that of 1-butene and was not resolved from the latter; however, the formation of isobutene by skeletal isomerization of 1-butene could be ruled out (see below). GC analyses allowed the determination of the overall mass of every component in the effluent. The mass balance was usually satisfied to > 99.7%. Conversion and selectivities were computed on a molar basis. They could be related either to 1-butene or to total butenes; in the former case, 2-butenes were taken as reaction products and the process was actually the sum of isomerization and oligomerization; in the latter case, all butenes were considered as unreacted reagents, so only oligomerization (both of the initial I-butene and of the 2butenes formed from it) was taken into account. Samples of liquid alkene products were hydrogenated under pressure (20 bar) over 5% Pd on carbon, obtaining a smaller number of species: the GC peaks corresponding to the C8 fraction were systematically identified, mostly by comparison with pure samples of octane isomers and all of them by GC-MS: this allowed the determination of the linear octene fraction and of the average degree of branching of the CR fraction [ 231 through a branching index defined as BI = [ Me,pentanes fraction] x 3 + [ Me,hexanes fraction] X 2 + [Me-heptanes fraction]. The hydrogenation procedure was checked on a few pure octene isomers, among which I-octene, and found to be reliable, without skeletal isomerization. An example of hydrogenated C, isomer determination is given in Table 2.

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Table 2 Hydrogenation r.t. (min) ca. 23.8 25.0-25.2 25.7-25.8 ca. 26.6 27.9-28.0 28.0-28.1 28.9-29.1 29.4-29.5 32.3-32.5

of the products of run B-l: GC analysis in the C8 region Corresponding octane isomer Sample L3 0.93% 8.32% 4.25% 0.65% 11.11% 2.47% 60.08% 10.05% 2.14% 1.89 Sample L5 0.94% 8.36% 4.27% 0.62% 11.23% 2.39% 60.06% 10.05% 2.08%

2Jdimethylhexane 2,4-dimethylhexane 3,3-dimethylhexane 2,3,4-trimethylpentane 2,3_dimethylhexane probably 3-ethyl-2methylpentane 3,4_dimethylhexane 3-methylheptane n-octane branching index BI =

1.89
h, on the average, with reference to

cat.B (501 mg); T= 180C; P=40 bar; W/F=28 g h/mol; at TOS 4248 total butenes: conversion 49%. C, selectivity 82%.

Gas analysis and liquid sampling were performed at time-on-stream (TOS) values of 18, 21, 24, 42, 45, and 48 h. This allowed the determination of the degree of stability of the catalyst, by comparison of its behaviour on the first and the second day on-stream. Usually values of fractional conversion and selectivities on the second day on-stream were fairly constant and were averaged. An example of the detailed analytical results on a given sample is shown in Table 3.
Table 3 Example of GC analysis during a run: sample at TOS 48 h of run A-12 (gas mass 125.46 mg/h; liquid mass 874.30 mg/h; total mass fed 999.77 mg/h) Fraction Found (mg/h) i-Butane n-Butane I-Butene 2-Butenes Total butenes CS C, C, C, Cg Cl0 C,, C12 C,, C 14f 1.126 2.498 32.119 296.853 328.972 0.443 1.118 1.441 545.768 2.1.5s 0.448 0.000 115.486 0.000 0.303 (mmol/h) 0.019 0.043 0.572 5.291 5.863 0.006 0.013 0.015 4.864 0.017 0.003 0.000 0.686 0.000 0.002 Reference: Fract. conv.

I -Butene
Select. 0.12% 0.26%

Reference: Total butenes Fract. conv. Select. 0.17% 0.37%

96.79% 30.68% 67.10% 0.05% 0.12% 0.15% 56.40% 0.22% 0.05% 0.00% 11.93% 0.00% 0.03% 0.07% 0.17% 0.21% 81.36% 0.32% 0.07% 0.00% 17.22% 0.00% 0.05% h, on the average, with reference to

cat.A (500 mg); 7= 140C; P= 80 bar; W/F=28 g h/mol; at TOS 4248 total butenes: conversion 67%. Cx selectivity 8 1%. Sum of gas and liquid analyses.

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3. Results and discussion Dimerization catalysts are also active for the isomerization of butenes. From a thermodynamic point of view, isomerization of 1-butene by double bond migration is favoured, since equilibrium constants evaluated for the ideal gas state [24] for the reactions lbutene F1 cis-2-butene and 1-butene F? trans-2-butene correspond to 2-butenesl l-butene equilibrium ratios of 18.3 at 370 K, 12.1 at 420 K, and 8.9 at 470 K, i.e. values well above unity for the temperature range of our runs. During the experimental runs, the actual ratios often approached the equilibrium value (in a few cases almost reaching it), showing that the isomerization activity of the catalysts was usually predominant over the dimerization activity. This justifies the current use of total butenes as reference for conversion and selectivities. Reference to total butenes would be correct even in the case of a partial skeletal isomerization of 1-butene to isobutene. However, in a run carried out by feeding isobutene instead of I-butene on one of our catalysts (cat. A, T= 18OC, P= 80 bar, W/F= 28 g hl mol) it was found that some of the most abundant peaks in the CC analysis referred to products different from those commonly found when feeding I-butene. Therefore, any isomerization of 1-butene to isobutene, followed by dimerization of the latter, would have been easily detected. Catalysts were used both as fresh samples and after regeneration, A comparison of the results of identical runs, on fresh and on regenerated catalysts, showed very similar levels of conversion and selectivity. Only a slight increase of the yield of C8 alkenes was noticed after regeneration of the catalyst or when comparing e.g. a catalyst after its fourth regeneration with a sample after the first regeneration. Few tests were directed at evaluating the effect of changing flow conditions. Two runs on catalyst A, at W/F= 14 g h/mol, T= 180C P = 40 bar, were carried out with different F-values (0.0178 mol/h for run A-4; 0.03 18 mol/h for run A-6) : results were similar, so that external diffusion effects may be considered negligible. Taking into account the values of the critical temperature and pressure of I-butene and 2-butenes, and the low volatility of reaction products, the reaction mixtures of most of our runs can be considered to be supercritical fluids at the reactor entrance and liquids down the reactor. In the analogous case of a previous research on the dimerization of I-butene over a nickel-exchanged X zeolite [ 251, evidence of a diffusion-controlled mechanism had been found. A change of time factor, of course, has a marked effect, as shown in Table 4. At increasing values of W/F, conversion increases and so does stability of the catalyst (smaller differences between first and second day on-stream), while dimerization selectivity decreases and the branching index of the C8 product fraction rises from 1.95 to 1.99. This shows that longer time factors favour both trimerization of butenes and formation of higher-branched dimers by isomerization. Most of the runs were carried out at a constant value of W/F (28 g h/mol), in order to compare different catalysts at different temperature and pressure values. When catalysts A, AS and B have been used at 180C in runs at 40 and/or at 80 bar, they proved roughly similar as to conversion, stability, and C8 selectivity, although differences indicate that AS is a less active catalyst, as shown in Table 5. It can be noticed that yields are higher at the higher pressure.

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Table 4 Runs on catalyst A (T= 180C; P= 40 bar; F= 17.8 mmol/h), and selectivities: total butenes W/F (g h/mol) Run no. Fractional conversion (I = 24 h) At TOS 4248 h: Fractional conversion Selectivity to C, alkenes Selectivity to C1* alkenes Within the C, hydrogenatedfraction: n-Octane 3-Me-heptane Me,-hexanes BI Branching index defined as 14 A-3 0.3 1 0.14 0.82 0.14 28 A-2 o.s4 0.49 0.77 0.18

at increasing

WIFvalues;

reference for conversion

56 A-l 0.82 0.78 0.58 0.28

0.48% 8.50% 86.29% 1.95

1.08% 5.65% 88.23% 1.97

0.38% 4.58% 90.72% I .99

[ Me,pentanes fraction] X 3 + [Me,hexanes fraction1 X 2 + [Me-heptanes fraction].

At a pressure of 80 bar, comparison runs were also carried out at lower temperatures: at 140C yields of C, alkenes [ Y] at TOS = 4248 h were in the following order: cat. A (run A- 12) (fract. conv. = 0.67; Y= 0.54) > cat. B (run B-7) (fract. conv. = 0.5 1; Y= 0.46) > cat. AS (run AS-4) (fract. conv. = 0.28; Y= 0.24) while at 120C a comparison limited to catalysts A and B gave: cat. A (run A- 13) ( fract. conv. = 0.62; Y = 0.48) > cat. B (run B-8) ( fract. conv. = 0.28; Y= 0.24) differences in yield being due mainly to differences in conversion. Remarkably, the activity of the catalysts is lowered in a different way when the temperature drops.
Table 5 Comparison of catalysts in standard runs (T= 180C; Wl F= 28 g h/mol); at TOS 4248 h P=40 bar Run no. Catalyst sample Fractional conversion Selectivity to C, alkenes Selectivity to C,? alkenes Yield of CR alkenes A-2 fresh 0.49 0.77 0.18 0.38 P=80 bar Run no. Catalyst sample Fractional conversion Selectivity to Cs alkenes Selectivity to C,, alkenes Yield of C, alkenes Regenerated catalyst, A-11 fresh 0.81 0.76 0.20 0.61 AS-5 regen. 0.5 1 0.87 0.11 0.44 B-5 fresh 0.65 0.89 0.10 0.58 B-9 regen. 0.73 0.83 0.14 0.60 B-l fresh 0.49 0.82 0.12 0.40 reference: total butenes; average values

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45

Analyses of the branching of octene isomers gave the results shown in Table 6. The values of the Branching Index (BI), not specified in the table, were in most cases large (> 1.87); the lowestvalues were: 1.85 (A-13); 1.84 (B-9); 1.75 (B-6); 1.66 (B-7); 1.49 (AS-4) ; 0.77 (B-S). When on a given catalyst different temperatures were tested, a regular increase of the linear C, alkene fraction has been recorded at decreasing values of r, since, on the other hand, conversion was obviously lower at lower temperature, the yield of noctenes did not increase to the same extent. Linear octenes were more abundant, in general, in runs at 80 than at 40 bar; therefore the most convenient condition for lineardimers proved to be high pressure and a relatively low temperature. However, a limit to lowering the reaction temperature is met, when considering the catalyst stability. By defining a Stability Index (SI) as fract. conv. ( t = 42-48 h) / fract. conv. (t = 24 h) , it has been found that, in a series of runs under analogous conditions, for each catalyst there is a range of temperatures where SI is close to 90-lOO%, but a temperature exists, below which SI falls to low values (Fig. 1). It seems appropriate to compare catalysts A, AS and B in the region where they are all stable, as has been done in Table 5 (runs at 180C). Looking in detail at the results of runs under a pressure of 80 bar, the activity order appears to be A > B > AS. This is also the
Table 6 Production of linear isomers of CR alkenes butenes; values on the second day on stream Catalyst T (C) Run no. A 120 140 180 200 140 160 180 120 140 160 180 180 100 180 180 n-Octane Y(n-C,) Run no. A-13 A-12C A-l Id n-Octane 3.6% 3.0% 2.4% Y( n-C*) 1.74% 1.62% 1.48% P=40 bar

(W/F=

28 g h/mol

unless otherwise

indicated);

reference:

total

P=80 bar

A-2d A-l

1.1% 0.5%

0.41% 0.24%

AS

AS-4 AS-3 AS-5 B-8 B-7C B-6 B-5d B-9

7.8% 0.9% 0.5% 36.6% 5.0% 2.5% 2.2% 3.0%

1.83% 0.34% 0.23% 8.90% 2.31% 1.18% 1.29% 1.81%

B-ld B-4 C-2d C-l D-l

2.1% 2.1% 23.6% 4.1% 23.8%

0.84% 0.97% 5.99% 2.14% 2.83%

n-Octane within the C, hydrogenated fraction, Yield of n-octenes, calculated from the yield of CI, alkenes and the fraction of linear isomers. Regenerated catalyst. dFresh catalyst sample. W/F=56 g h/mol.

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order of surface acid titer of the catalysts (Table l), when measured both for strong acid sites (pK,< - 3.7) and for medium-to-high strength acid sites (pK, < 1.5). The surface acid titer, as determined by the aluminium content of the zeolite, seems to control the greater activity of catalyst A with respect to B. As to catalyst AS, silylated with hexamethyldisilazane, it can be argued that, besides restricting the pore mouth width, so reducing the catalyst activity by hindering the access of reactant to the inner sites, the HMDS molecule could have penetrated, at least in part, inside the pores, so reducing the tetrahedral aluminium content and therefore the overall surface acidity of the zeolite (see data in Table 1). For the same runs at 80 bar (Table 5) one can appreciate that the overall selectivity to C, and C,* alkenes falls in the range 0.96-0.99; within these overall values, the higher activity of catalyst A corresponds to higher Cl2 and lower Cx selectivity, as expected for consecutive reactions. The low-Al catalyst B presents a higher level of C, selectivity, both at 80 and at 40 bar, with a small loss of activity (80 bar) or no loss at all (40 bar). From this point of view, the silylation of A does not prove really effective, since it gives to catalyst AS about the same CX selectivity of B, but at the expense of a lower activity. Standard runs at 18OC, although useful for the above comparison of activities and selectivities, were not interesting for the production of linear dimers (Table 6) and this suggested to perform runs at lower temperatures, with better results in terms of lower degree of branching of the dimers, as already discussed. To compare our catalysts, on this point, with some whose behaviour had already been published, tests have been done on catalysts C (NiO-Al,O,/SiO,) [ 191 and D (Coo/C) [ 31 and results are reported in Table 6. Values of the Branching Index BI were found to be: 1.79 (C- 1) ; 0.99 (C-2) ; 0.95 (D- 1) . WhiIe the behaviour of catalysts C and D, under conditions similar to those indicated by the respective authors, is confirmed to be good in terms of linear dimers, it can be noticed that catalyst B, at 120C and 80 bar, seems even better. Unfortunately, this good behaviour is only observed under conditions where the conversion values are low, a fact which reflects in low values of the yields of n-octenes, in the range from 5 to 10% in the best cases. Fig. 2 shows (for catalyst B at constant time factor) how lower temperatures cause lower overall

100

110 120
(t=42-48

130

140

150

160

170

Temperature PC) Fig. 1. Stability Index [SI=fract. B ( + ) as a function of temperature cow. h)/fract. cow. (t=24 h)

] of catalysts A

(W), AS (0)

and

(runs at 80 bar; W/F=

28 g hlmol).

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Catalysis A: General 110 (1994) 3948

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0.6 --

120

130

140

150

160

170

Temperature&Z

Fig. 2. Yields to total ( W) and linear (0)

C, alkenes in runs on catalyst B at 80 bar (W/F=

28 g h/mol)

Cs yields, but higher linear Cs yields than those observed in runs at 180C. Catalyst AS, similar to B as regards the surface acidity, could not be tested at temperatures less than 14OC, owing to its instability (Fig. 1). Run B-8, the best case, gave an interesting result as to the molar ratio 2-butenes/ 1-butene in the effluent: such a ratio was around 2 on the first day on-stream and around 0.3 on the second day, against an equilibrium value of 15 at 390 K. So, high selectivity to linear dimers is associated with low conversion in the butene isomers equilibration. The latter observation suggests that a prerequisite for obtaining linear dimers is that 1-butene must not isomerize to 2-butenes. Under conditions that limit the carbenium ion mechanism and favour the coordinative mechanism of dimerization on nickel [ 191, I-butene is likely to give less branched dimers and the latter are more able to avoid further isomerization. The typical shape selectivity of ZSM-5 zeolites does not seem to play an important role in this case, since the blocking of external acid sites (silylated catalyst AS), which should have enhanced any shape-selectivity effect, did not give particularly good results. The reaction to linear (or at least to less branched) dimers seems to depend on a correct balance of the dimerization and isomerization activities of a catalyst that combines metal (Ni) and acid centres.

4. Conclusions I-Butene has been contacted with some catalysts based on nickel and ZSM-5 zeolite, finding good levels of conversion. Two main processes compete: isomerization to 2-butenes and dimerization to octene isomers; in addition, 2-butenes are also able to dimerize. Other reactions are present, in particular the formation of trimers (Cr 2 alkenes) . From the point of view of the yields of C, alkenes, catalysts of ZSM-5 exchanged with nickel and not silylated (A, B) proved to be more active than a silylated sample (AS). As to the yields of linear octenes, the best results were obtained in runs at 80 (rather than 40) bar, and at relatively low temperature ( 120-140C were required in order to obtain 2 3%

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of linear isomers in the C, alkene fraction), the best result (ca. 37% of linear isomers) was obtained with catalyst B, based on a low-alumina ZSM-5 zeolite.

Acknowledgements We acknowledge Praoil SpA for GC-MS identification of the alkene fractions of different C number in the reaction product. Thanks are due to Dr. Casalini for GC-MS identification of the C, alkane isomers from the hydrogenation of the product.

References
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