ELSEVIER ‘The Chemical Engineering Journal 63 (1996) 27-36 THE CHEMICAL ENGINEERING JOURNAL Hydrogenation of naphthalene with platinum—aluminium borate catalysts Ting-Chia Huang *, Ben-Chang Kang Deparment of Chemical Engineering, National Chang Kung University, Tainan 701, Taiwan Received 28 April 1995; accepted 30 October 1995 Abstract Naphthalene dissolved in n-hexadecane was used as a model compound to simulate the aromatics in diesel fuels for hydrogenation activity test aluminium borate catalyst (Pt-ABx) is higher than that of ‘The aluminium borate (ABx) supports were prepared by the coprecipitation method. The aromatic hydrogenation activity of Pt/ t~7-Al,O, catalyst, but its cis-decalin selectivity is lower than that of Pt~y-Al,O3 catalyst owing tothe higher acidity of ABx than 7-Al,O3 support. When the AL:B atomic ratio decreases, the hydrogenation and hydrogenolysis activities of Pt-ABx catalyst increase but the cis-decalin select ‘When boron is added to the Pt-7-Al,O, catalyst to give Pt-Br- the cis-decalin selectivity since the acidity of the support increas lecreases ), catalyst, it improves the catalyst hydrogenation activity but reduces es. However, the hydrogenation activity of Pt-Bx-Al,0; cataly 5 deceases ‘when the ALB ratiois smaller than 8. The Pt-Br-Al,O; isa better aromatic hydrogenation catalyst than Pt-AB, catalyst since its hydrogenolysis activity is lower, ‘Keywords: Aluminum borate; Bi-aromati; Hydrogenation; Naphthalene; Tetrali; Selectivity 1 Introduction ‘The hydrocarbon liquids from the treatment processes of heavy oil or residue oil contain a large amount of aromatic compounds (mainly polyaromatics) and a significantamount of heteroatoms such as sulphur, oxygen and nitrogen. These hydrocarbons have to be hydrotreated to improve the hydro- ¢gen-to-carbon ratio and the heteroatoms have to be removed for fuel oil. A high aromatics content in diesel fuel lowers fuel quality and contributes significantly to the formation of undesired emissions in exhaust gases [1-3] In recent years, considerable attention has been paid to finding new catalysts and developing the processes of satu- ration of aromatics for diesel fuel. The most well-known process for aromatic saturation uses conventional hydrotreat- ing catalysts (sulphided CoMo~y-Al,0; ot NiW-y-Al,0s) in the first-stage operation and noble metal catalysts in the second-stage operation [4]. Noble metal catalysts are known to be deactivated rapidly by the adsorption of sulphur-containing compounds which are present in industrial feedstocks [5]. Therefore, a severe pretreatment is necessary to reduce the sulphur content to a level that does not affect the performance of the noble metal catalysts [6]. Extensive research has been carried out to * Comesponding author. 13-0467/96 $15.00 © 1996 Elsevier Science S.A. All rights reserved develop sulphur-tolerant noble metal catalysts by various cat- alyst manufacturing companies such as Shell Co., Criterion Co., Amoco Co. and Topsoe Co. Noble metals (e.g. Pt or Pd) on zeolite catalysts have been used in recent years as aromatics hydrogenation catalysts [4,7,8] Generally, hydrogenation noble metal catalysts have been supported on }+AL,Os, activated carbon, SiO, and SiO,- ‘Al,0, [9-12]. Recently, some studies have indicated (13~ 15] thatthe nature of the support might play a significant role. in determining catalytic activity. Explanations have been given in terms of the interactions between the metal crystal- lites and the support. Aluminium borate has been reported to be a good catalyst and a good support material for various reactions. Pine [16] employed alumina-boria as a catalyst in the hydrocarbon conversion process. Tanabe [17] showed that alumina-boria catalysts could be used as cracking catalysts. Tsai etal. [18] showed that aluminium borate was a good support for hydro- desulphurization catalysts. Chen and Li [19] found that the Pt-aluminium borate catalyst had high activity for hydrogen- ation of cyclohexene at atmosphere. Therefore, itis valuable to study in greater detail Pt-aluminium borate catalysts for aromatic hydrogenation. In this study, the incipient wetness impregnation method and coprecipitation method were used to prepared two dif- ferent series of aluminium borates with different ALB atomic2% T.-C. Huang, BC. Kang /The Chemical Engineering Jounal 63 (1996) 27-36 ratios, Naphthalene dissolved in n-hexadecane was used as a ‘model compound to simulate the aromatics in diesel fuels for the hydrogenation activity test. Hydrogenation of naphtha- lene (biaromatic) over noble metal supported on alumina and aluminium borate were tested and compared in a trickle bed reactor at high pressure (5.17 MPa). The chemical and physical properties of these catalysts were characterized to correlate with their catalytic properties. The selectivity of cis- Pd>Rh>Ru>Ir. Rh-Al,Os, Ru-Al,O3 and I-Al03 Support and Surface area Pore volume, ‘Average pore Meta catalyst (mg) (omg) radius (nim) dispersion (1) Fresh support 1989 0.658 658 (2) Prepared catalyst PeB=ALO, 195.0 0.668 662 0924 PLB64-ALO, 1895 ons 613 0.899 Pe-B32-AL0; 189.4 0.686 619 0897 PLBI6-AL0, 1922 0716 646 0.832 PL-BB-ALO, 94 0.552 138 0.752T.-C, Huang, B.-C, Kang / The Chemical Engineering Journal 63 (1996) 27-36 31 Table3 Comparison of the characteristics of different supports and catalysts Suppor Surface area Pore volume Average pore Metal (a? gy) (omg!) radius (nm) dispersion (a) ce81-4 (1) Fresh support 1989 0.658 658 (2) Prepared catalyst, 1980 0.68 6a 0924 (8) ABS (1) Fees support 2666 0470 all (2) Prepared catalyst ms4 oes 291 ost (©) Alza (1) Fresh support 1950 0487 456 (2) Propared catalyst 1798 0509 467 0639 (D) APR (1) Fresh suppoct 218 0316 73 (2) Prepared catalyst 1980 0903 4 ono (®) ABSAPIO Prepared catalyst 1780 ost 644 aBi6aPI6 Prepared catalyst 1989 0316 52 2 -—— — tested Rh-Al,0; catalyst at low temperature, and the hydro- 2 WW __ aA) zgenation activity of Rh~Al,O, catalyst was even higher than 2 We that of Pt- Al,O; catalyst. However, Rh-AL,O, catalyst had ¢ similar hydrogenolysis activity which consumed more hydro- g | gen and its hydrogenation activity was also quickly de- 3 center J activated. — g Koussathana et al. [32] obtained the same result that plat- /R inum is the most active metal for the hydrogenation of aro- (o) PI/BI8AIs ‘matic compounds under this reaction condition, followed by rhodium and ruthenium. Therefore, platinum was used in the 2 following to test the effect of supports, é 3 3.3. The effect of Al:B on the activity of Pt-Br-ALOy * catalysts 3 center The hydrogenation of naphthalene reaction might be . — described as follows [33]: 0 WR (2) PAB a rf (a) Pt/cs~3s1~4 Fig. 4. The Pt metal profiles of the catalysts: (a) PL-Cs-331-4; (b) P= ABBS; (c) P-BIGALOs relative intensity not only had high initial hydrogenation activity but also had high hydrogenolysis activity and rapid deactivation rate. We cis-decalin eT vet Le | In the following study, the naphthalene was completely hydrogenated to tetralin forall catalyst activity tests, except for catalysts Pt-AlZn9 and Pt-B8-Al,0, ‘The experimental reproducibility was checked with differ- ently prepared batches of Pt-ABS catalysts at 493 K and 5.17, MPa, The differences between mole fractions of products with different batch catalysts were no more than 2%. There- fore, the reproducibility was good. To check the influence of AI:B atomic ratio on the hydro- genation activity of Pt-Bx-Al,0, catalysts, a series of Pt~ Bx-AlO, catalysts were prepated with different ALB 42k, naphthalene o)2 TC. Huang, BC. Kang /The Chemical Engineering Journal 63 (1996) 27-36 3 > g 8 & time(min) Fig. 5. The hydrogenation activity of diferent noble metals supported on ‘AljO, at 533 K and 5.17 MPa. wp 1p a" =< 3 i 3 et | 1 a i & é qf : | 0 2 40 60. 80 = AI/B atomic ratio Fig. 6. The effec of ALB on the hydrogenation aatvity of Pt-B1-Al,0, catalyst. 7=493 K, P=5.17 MP. compositions. Their activities and selectivities at 493 K, 5.17 MPa, and stable activity state (after 800 min of reaction) are shown in Figs. 6 and 7 respectively. When the boron was, inserted into Pt~y-Al,O catalyst, the hydrogenation activity of the catalyst increased. The Pt metal distribution of Pt B16-AI,0, is more uniform than that of Pt-Al,O3,as shown in Fig. 4, Therefore, the higher hydrogenation activity of Pt- B16-Al,0, is not due to the metal distribution of catalyst. According to the results of Li and Chen [27], the acid strength of the support was increased dramatically on going from alumina to B20-Al,O, (AI:B = 20). However, a further increase in boron content does not increase the acid strength of the catalyst. That is why adding boron toPt-y-Al,0, would increase hydrogenation activity. This willbe discussed in the following section. Too much boron (ALB <8) is poisonous to the hydrogenation activity of catalyst, as shown in Fig. 6. At lower boron loadings, a surface mixed oxide of alumina~ borate is formed. However, at higher boron loadings, borate (B,0s) itself is formed in the support surface [26]. This is ‘why too much boron is poisonous to the hydrogenation activ- ity. According to Fig. 6, the optimal amount of boron in Pt— Br-Al,Os catalysts forthe hydrogenation activity is such that ALB~20. Adding boron to Pt-Al,O; catalyst is unfavourable for the selectivity of cis-decalin in naphthalene hydrogenation, as shown in Fig. 7: the greater the amount of boron in the Pt Bx-Al,0; catalyst, the lower was the selectivity of cis decalin. For high boron contents of Pt-Bx-Al,O, catalyst, the reason for the decreasing selectivity of cis-decalin is sim- ilar to that of the Pt-ABx catalyst owing to the increase in support acidity, as discussed in the following. 3.4, The effect of Al:B ratio on the activity of Pt-ABx catalysts To check the influence of AI:B ratio on the hydrogenation activity of PL-ABx catalysts, a series of activity tests were carried out in the continuous reaction system (Fig. 1) with different Pt-ABx catalysts, The hydrogenation activity and cis-decalin selectivity of catalysts were compared at the steady state (after 800 min of reaction). The experimental results for Pt-ABx catalysts are shown in Fig. 8. It is shown. that Pt-ABx catalysts have completely saturated naphthalene at 493 K, 5.17 MPa, except for Pt-AB16 and Pt-AB~, ‘The ABee support was made by the same method as ABx ‘without adding boric acid, The hydrogenation activity of Pt- ABeo catalyst is lower than those of other Pt-ABx catalysts. From the results of Peil et al, (24], the surface acid strength is increased dramatically on going from pure alumina to an aluminium borate with an AI:B ratio of 20, An increase in the boron content of ABx support increases the acid strength, and a maximum acid strength is reached at Al:B = 5. Accord- ing to the results of Wang and Chem [34], the acid concen- ost Xu/Xea 08 08 °°9 20S 41/8 atersée ratio Fig. 7. The effec of ALB on the selectivity of cis-decalin for Pr-Bs-Al:Os catalyst, 7=.493 K, P= 5.17 MPa. Xq mole fraction of cisdecalin; Ky, mole faction of zrans-decalinTC. Huang, BC. Kang /The Chemical Engineering Journal 63 (1996) 27-36 3 100-00 1005 leo mote frac, of total-decatin (2) mole frac. of n-haxedecane hnydrogenaysis (3 AI/B atomic ratio Fig. 8. The effect of ALB on the hydrogenation activity of Pt-ABx catalyst 33K; Pe 5.17 MPa, tration increases with increasing boron contents of the ABx supports. The ABx supports have nearly the same surface atea and pore size, and the Pt-ABr catalysts have nearly the same metal dispersions, as shown in Table 1. Therefore, the increasing hydrogenation activity of Pt-ABx catalyst with increasing boron content of ABx support is due tothe increas- ing acidity of the support, At the same time, the hydrogen- olysis activity of Pt-ABx catalyst also increases with increasing boron content. Because the acid strength of Pt- Br-Al,0; catalyst is intermediate and lower than that of Pt- ABx [27], no hydrogenolysis is observed for Pt-Bx-Al,O5 catalyst under the same reaction conditions ‘The influence of AL:B ratio of Pt-ABx catalysts on the selectivity of cis-decalin was obtained from the same exper- iments, as shown in Fig. 9: the greater the amount of boron in the Pt-ABx catalysts, the lower was the selectivity of cis- decalin. According to reaction sequence (1), trans-decalin can be obtained by the direct hydrogenation of tetralin or by isomerization of cis-decalin. At complete saturation, cis- decalin can continue to isomerize to trans-decalin until it approaches equilibrium. Lin and Vannice [35] proposed a model that aromatics adsorbed on acid sites in the metal-oxide interfacial region could react with hydrogen that had spilled over from the metal surface. Consequently, more acid supports will give an addi- tional contribution to the overall activity. The catalyst with high acidity of supports will give high hydrogenation activity. ‘Therefore, the lower is the AL:B ratio of a Pt-ABx catalyst, the higher is the hydrogenation activity, and the hydrogena- tion activity of catalyst Pt-Bx-Al,0s is higher than that of Pt-y-Al,O,, as shown in Figs. 8 and 6, Aromatics adsorbed on an oxide surface appear to have a a bond interaction similar to that on a metal (Pt) surface; however, the bond strength is lower than on the metal surface [35]. According to the reaction steps suggested by Weitkamp {20}, tetralin can react directly with hydrogen to form cis- decalin or through the intermediates octalins. However, tetralin cannot convert directly into trans-decalin; itneeds to go through A?®-octalin and then to trans-decalin For low ALB atomic ratio of the catalyst Pt-ABx, more aromatics are hydrogenated through the metal oxide interfa- ciel region owing to the high acidity of the support. Because of the low bond strength between octalin and interfacial sites, more octalins are desorbed and adsorbed again, and then more, trans-decalins are produced. Therefore, the selectivity of cis- decalin is low for alow ALB atomic ratio of Pt-ABx and Pt- Bx-Al,0, catalysts, as shown in Figs. 9 and 7, Alternatively, low ALB atomic ratios of the Pt-ABx and Pt-B1—Al,0, cat- alysts provide the high hydrogenation activity of catalysts and more cis-decalin continues to isomerize to trans-decalin. Hence, these catalysts have low selectivity of cis-decalin More experiments have to be done to determine which one of the reasons is important, 43.5. The effect of temperature on the activity of Pt-ABx and Pt-Al,O, catalysts To investigate the inffuence of temperature on the hydro- genation activity of Pt-ABr and Pt-Al,0; catalysts, experi- ‘mental tests were conducted at three different temperatures, 473 K, 493 K and 533 K. The experimental results for Pt- ABIO and Pt-Al,O, catalysts are shown in Figs. 10 and 11 the higher the reaction temperature, the quicker the rate of hydrogenation. However, when the reaction temperature increases, the selectivity of cis-decalin decreases. Itis assumed thatthe reaction ate is controlled by a surface reaction step. According to the results of Huang and Kang (331, X=exp[— (he! +h) 1] (2) where X; is the mole fraction of tetralin, ris the space time, Jy! is equal to k,Py?, ks is equal to ksPy,” and kp, ky are the rate constants, as shown in Eq. (1). By applying Eq, (2) to “—— \ @ 1 1 @ AI/B atomie ratio Fig. 9, Theeffectof Al:Bon the selectivity of is-decalin for PL-ABx catalyst T=493K, P=5.17 MPa. X. mole faction of cis-decalin;Xy, mole faction of rans-decain34 TC, Huang, B-C. Kang /The Chemical Engineering Journal 63 (1996) 27-36 mote fraction of total-decatin (s) mote fraction of tran-decatin. () Fig. 10. Theeffectof temperature on the hydrogenation activity for P-ALLO, at P=5.17 MPa: —, mole fraction of total dealin; ~~ mole fraction of 93K; A, T=533 K. mole fraction of tran-decalin (x) pts Noy ‘0-200 400~—600—~800 7268 time(min) Fig, 11. Th effect of temperature on the hydrogenation activity for Pt-ABLO at P=5.17 MPa: —, mole fraction of total dealin; ~~~, mole fraction of trans-ecalin; O, 7=473 K; 0, T= 493 K; A, T=533 K. the experimental data in Figs. 10 and 11, the sums i! +3! of rate constants and activation energies of Pt~AB10 and Pt— Cs-331-4 (PLALO,) catalysts were calculated and are shown in Table 4, Table 4 shows that the specific hydrogenation activities of Pt-AB10 are higher than those of Pt-Cs-331-4, at tempera tures between 473 K and 493 K. The activation energy of Pt— Cs-331-4, 13.6 keal mol” is similar to the results of Lin and, Vannice [32] and Bassetetal. [36]. However, the activation, energy of tetralin hydrogenation for Pt-AB10 catalyst, 19.3 kcal mot™', is higher than that of Pt~Cs-331-4. For the Pt- AB10 catalyst, there are two reaction paths for hydrogenation of aromatics. One is the same as for Pt-Cs-331-4 catalyst, that aromatics adsorb on the metal surface and react with hydrogen. The other is that aromatics adsorb on acid sites in the metal-oxide interfacial region and then react with hydro- gen pilled over from the Pt metal surface. The latter path has a higher energy barrier than the former. Because tetralin is a Jarger molecule than benzene and the aromatic ring of naph- thalene near the metal has first been hydrogenated, the dis- tance of hydrogen spill-over in tetralin hydrogenation longer than in benzene hydrogenation. Therefore, the acti- vation energy of Pt-AB10 obtained in this study is higher than the results of Lin and Vannice [35] for Pt-Al,O3 catalyst and for Pt-Cs-331-4 catalyst in this work. If the activation energy is larger than 6 keal mol~', it may imply that the operation is in a reaction-controlled region, [37]. The data in table 4 confirm the assumption that the reaction is kinetically controlled. 3.6, The influence of support's acidity on the performance of catalysts For the more homogeneous metal distribution and in order to neglect the particle diffusion resistance, a small size ofthe supports (25~45 mesh) was used to prepare catalysts [33]. ‘The catalysts’ hydrogenation activities were tested at a tem- perature of 533 K and pressure of 5.17 MPa, and the results, are shown in Fig. 12. According to the results of Tanabe etal. [29], Li and Chen (27) and Wang and Chen [38], the acidity sequence of supports is AB3.5> AAP8c> 7-Al,03 (Cs-331-4) > AIZn9. From the results of Fig. 12, the hydrogenation activity of catalyst Pt-AlZn9 is much lower than those of Pt-AB3.5, Pt— AAP8c and Pt~y-Al,03. Because the diffusion resistance can be neglected, the reason for the low hydrogenation activity of catalyst Pt-AlZn9 is the low acidity of AIZn9 support and ow metal dispersion, as shown in Table 3, From Fig. 12, Pt- ‘y-Al,O;, PI-AAPSc and Pt-AB3.5 catalysts have completely saturated naphthalene, but catalysts Pt-AB3.5 and Pt-AAP8e have the lowest selectivity of cis-decalin. Because the more homogeneous metal distribution is obtained owing to the use of small particle impregration, the reasons for low cis-decalin, selectivity are the high acidity and high activity of Pt-AB3.5 Table + Kinetics of tetzalin hydrogenation over Pt catalyst at 5.17 MPa Catalyst kf thy! bo) z ‘Specific rate constant (keal mot!) 4BK 493K 4BK 493K PHCs.331-4 347 513 136 342 618 PL-ABIO 692 1581 193 854 1951TC, Huang, BC. Kang /The Chemical Engineering Journal 63 (1996) 27-36 35 oaagee — 20 ~ 9 9 - o- mote fraction of total-decalin (#) mote fruction of tran~decalin (4) dy 0 200 400 408 time(min) Fig, 12. The effect of suppor acidity onthe hydrogenation activity (T=533, K,P=5.17 MPa): — mole fraction of total decalin; ~~, mole fraction of trans-decalin; O, Pt-Cs-331-4; 0, PH-AB3S; 4, PL-AIZN9; ©, Pe ‘AAPSc. 119 ett mole fraction of total-decatin (%) mole fraction of trans-decalin (x) time(min) Fig. 13, The hydrogenation activity of PL-ABXAPy catalysts (T=513 K, P=5,17 MPa): —, mole fraction of total decalin; ~~, mole fraction of| trans-decalin; O, Pt-ABS; ©, Pt-ABI6; A, Pt-ABIGAPI6; ©, P- ABSAPIO, catalyst. The cis-decalin selectivity of catalyst Pt-AAP8c is lower than Pt~7-Al,03 for the same reasons. 3.7. The activity of Pt-ABxAPy catalysts ‘The activity and stability of Pt-ABx catalysts are very good, but their pore sizes are too small, as shown in Table 1 To improve its particle diffusion and to enable its application tothe hydrogenation of large aromatic molecules, aluminium phosphate was added to ABx supports to prepare ABxAPy supports. The pore sizes of catalysts Pt-ABSAP10 and ABI6API6 are larger than that of Pt-ABS, as shown in Fi 3 ‘The hydrogenation activity of catalysts Pt-ABXAPy are as good as that of catalysts Pt-ABx, and the Pt-ABI6API6 is even better than Pt-AB16 catalyst, as shown in Fig. 13. Therefore, the catalyst Pt-ABxAPy can be used for hydro- genation of large molecular compounds. 4. Conclusion Platinum is the optimum noble metal for the hydrogenation of aromatic compounds. The hydrogenation activities of Pt— ABx and Pt-Bx—Al,0, catalysts are higher than that of Pl-y- Al,0;, but the cis-decalin selectivities of Pt-ABx and Pt-Bz— ALO; catalysts are lower than that of Pt-y-AlO; owing to the higher acidity of supports. Because the acid strength of Pt-Bx-Al,05 catalyst is intermediate, a good liquid product yield for hydrogenation of aromatics in fuel oil can be obtained with reasonable hydrogen consumption. Therefore, the Pt-Br-Al,O, catalyst is a better aromatic hydrogenation catalyst than the Pt-ABx catalyst. ‘As the boron content in the Pt-ABx catalyst increases, the hydrogenation «ind hydrogenolysis activities become higher. However, the cis-decalin selectivity of Pt-ABx catalyst is reduced by the increasing boron content. When boron is, added to Pt-y-Al,0; catalyst, it improves the catalyst hydro- genation activity. However, too much boron (Al:B=8) degrades the hydrogenation activity. The high hydrogenation activity and low cis-decalin selectivity of Pt-ABx and Pt- Bx-Al,0, catalysts are reasonably explained by the model suggested by Lin and Vannice [15]. More researchis needed to study the effect of hydrogen spill-over on the hydrogena- tion activity Acknowledgement ‘The authors wish to express their gratitude for the support of this work by the Refining and Manufacturing Research Centre of Chinese Petroleum Corporation, References [1] BG, Barry, LJ, McCabe, DH. Gatke and JM. 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