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Kinetics and Mechanism of Benzene Hydrogenation over Supported Ru, Cu and Ru-Cu Catalysts

M.C. Schoenmaker-Stolk

Delft University Press

TR diss 1516

Kinetics and Mechanism of Benzene Hydrogenation over Supported Ru, Cu and Ru-Cu Catalysts

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Kinetics and Mechanism of Benzene Hydrogenation over Supported Ru, Cu and Ru-Cu Catalysts

Proefschrift Ter verkrijging van de graad van doctor aan de Technische Universiteit Delft, op gezag van de Rector Magnificus, prof.dr. J.M. Dirken, in het openbaar te verdedigen ten overstaan van het College van Dekanen op dinsdag 9 december 1986 te 14.00 uur door MARTINE CAROLINE SCHOENMAKERSTOLK geboren te Diemen scheikundig doctorandus

TR dss 1516

Dit proefschrift is goedgekeurd door de promotor Prof.dr. J.J.F. Scholten

Het onderzoek werd uitgevoerd met financile steun van de Nederlandse Organisatie voor Zuiver Wetenschappelijk Onderzoek, als onderdeel van het programma van de Stichting Scheikundig Onderzoek in Nederland.

Aan mijn ouders Aan Jan-Willem

CONTENTS

1.

GENERAL INTRODUCTION 1.1 Cyclohexane in t h e manufacture of Nylon 6 1.2 e-Caprolactam production via cyclohexene 1.3 Scope of the p r e s e n t t h e s i s References

1 1 1 2 3 5 5 6 7 7 7 8 10 13 13 11 21 28 28 28 31 31 32 33 33 31 31 35

2.

GAS-PHASE HYDROGENATION OF BENZENE OVER RUTHENIUM-ON-SILICA Abstract 2.1 I n t r o d u c t i o n 2.2 Experimental 2.2.1 M a t e r i a l s 2.2.2 Catalyst characterization and adsorption measurements 2.2.3 Hydrogenation equipment 2.2.1 Catalyst preparation and characterization 2.3 Results 2.3.1 Adsorption measurements 2 . 3 . 2 K i n e t i c s of the hydrogenation of benzene, 1 ,1-cyclohexadlene and cyclohexene 2 . 1 Discussion 2.5 Conclusion Acknowledgements References

3.

GAS-PHASE HYDROGENATION OF BENZENE OVER COPPER-ON-SILICA Abstract 3.1 I n t r o d u c t i o n 3.2 Experimental 3.2.1 M a t e r i a l s 3.2.2 Catalyst characterization 3 . 2 . 3 Hydrogenation equipment 3.2.1 Catalyst preparation

3.3 Results 3.3.1 Catalyst characterization 3.3.2 Kinetics of the hydrogenation of benzene 3.3.3 Temperature dependence of the hydrogenation rates of 1,4-cyclohexadiene and cyclohexene 3.1 Discussion 3.^.1 Kinetics of the hydrogenation of benzene, of 1,4-cyclohexadiene and of cyclohexene 3.4.2 Tanaka-Tamaru plots Acknowledgements References GAS-PHASE HYDROGENATION OF BENZENE OVER SILICA SUPPORTED Ru-Cu CATALYSTS Abstract 4.1 Introduction 4.2 Experimental 4.2.1 Materials 4.2.2 Catalyst preparation 4.2.3 Texture and surface composition 4.2.4 Hydrogenation equipment 4.3 Results and discussion 4.3.1 Catalyst characterization 4.3.2 XPS/AES surface analysis 4.3.3 Stability and activity of the catalysts in the benzene hydrogenation 4.3.4 Kinetics of the hydrogenation of benzene 4.4 Conclusions Acknowledgements References Summary Samenvatting Nawoord Curriculum vitae

36 36 38 42 44 44 17 19 50

51 51 52 54 54 55 56 57 57 57 62 63 67 67 68 68 70 73 76 77

C H A P

T E R 1

GENERAL INTRODUCTION

1.1 Cyclohexane i n the manufacture of Nylon 6 In t h e chemical i n d u s t r y benzene i s widely used as a raw m a t e r i a l [ 1 ] . I t i s e . g . hydrogenated on a very l a r g e s c a l e t o give high p u r i t y cyclohexane, which i s an important i n t e r m e d i a t e in t h e manufacture of Nylon 6. Cyclohexane i s present in petroleum, i n the naphtha f r a c t i o n , but i t s s e p a r a t i o n by d i s t i l l a t i o n t o s u f f i c i e n t p u r i t y i s too d i f f i c u l t and c o s t l y . A b e t t e r r o u t e t o cyclohexane involves reforming of naphtha over a platinum c a t a l y s t , l e a d i n g a f t e r d i s t i l l a t i o n t o high p u r i t y benzene, which i s then hydrogenated t o cyclohexane [ 2 ] . In the hydrogenation of benzene t o cyclohexane o f t e n n i c k e l and platinum c a t a l y s t s are employed. The r e a c t i o n proceeds over t h e s e c a t a l y s t s under mild c o n d i t i o n s (2-1 MPa and 110-600 K) with cyclohexane as the only product. As a l r e a d y mentioned, cyclohexane i s an i n t e r m e d i a t e in the p r e s e n t r o u t e s t o Nylon 6. Cyclohexane i s oxidised by oxygen over a c o b a l t or magnesium c a t a l y s t to a mixture of cyclohexanol and cyclohexanone [ 3 ] , the cyclohexanone being converted with hydroxylamine s u l p h a t e t o cyclohexanone oxime. Via a Beckmann rearrangement in the presence of s u l p h u r i c a c i d , E-caprolactam, t h e monomer of Nylon 6, i s formed from t h i s oxime [ 1 ] . 1.2 e-Caprolactam production v i a cyclohexene In our l a b o r a t o r y Don [5] and van der Steen [6] have i n v e s t i g a t e d the c a t a l y t i c p a r t i a l hydrogenation of benzene t o cyclohexene in the gas-phase, within t h e framework of the development of a cheaper process r o u t e t o e-caprolactam. By converting benzene t o cyclohexene, which can be oxidised over a Wacker c a t a l y s t t o cyclohexanone, the hydrogen consumption can be reduced by 33$ with r e s p e c t t o t h e hydrogen consumption of the present r o u t e s . The cyclohexane formed in the hydrogenation s t e p besides cyclohexene can be dehydrogenated t o benzene and r e c i r c u l a t e d t o t h e r e a c t o r . This dehydrogenation of cyclohexane over platinum i s a s e l e c t i v e p r o c e s s , which proceeds a t t e m p e r a t u r e s between 570 and 750 K [ 7 - 9 ] .

2
The investigations by Don [5] and by van der Steen [6] on the partial hydrogenation of benzene were performed using ruthenium catalysts. They showed that the cyclohexene selectivity is sufficiently high, but the yield of cyclohexene over ruthenium is still too low for industrial application. Don and van der Steen increased the cyclohexene selectivity by adding a modifier to the feed of the reactor. The modifier, for instance water, dlethylene glycol or E-caprolactara, interacts with the cyclohexene molecules on the metal surface via hydrogen bonds, which leads to a weakening of the cyclohexene adsorption bond and to lowering of the rate of hydrogenation to cyclohexane, resulting in a higher cyclohexene concentration in the gasphase. This "interception theory" has been amply described by van der Steen [6]. 1.3 Scope of the present thesis In support of the investigations on the partial hydrogenation of benzene we have given attention to the kinetics of the catalytic hydrogenation of benzene and of the reaction intermediates 1,4-cyclohexadiene and cyclohexene, in order to elucidate the reaction mechanism. Furthermore, we have studied the catalytic performance of copper and ruthenium-copper in detail. In the literature little agreement exists about the mechanism, and opinions differ on several points [10-20]: - adsorption of both reactants on the catalyst or of one reactant only. - competitive adsorption of the reactants or adsorption at different sites. - sequential (step-wise) or simultaneous addition of adsorbed hydrogen atoms to benzene. - addition of atomic hydrogen or of hydrogen molecules. - various opinions on the rate-determining step. On the basis of our kinetic measurements we suggest a step-wise mechanism for the hydrogenation of benzene over ruthenium, with a shift of the ratedetermining step at higher temperatures. This mechanism is amply discussed in Chapter 2. Further, on the basis of the adsorption enthalpies of benzene, 1, 'J-cyclohexadiene, cyclohexene and cyclohexane, a diagram is given of the reaction free enthalpy as a function of the extension of the reaction over a silica-supported ruthenium catalyst.

3
In Chapter 3 the preparation is described of two coppeion-silica catalysts, according to two patents, as well as the thoroughly investigated texture and surface composition of these catalysts. In order to compare the behaviour of copper in the hydrogenation of benzene with that of ruthenium, the kinetics over one of the copper catalysts was studied extensively. The activities of several transition metals in the hydrogenation of benzene were intercompared by plotting these activities in the form of Tanaka-Tamaru plots (volcano curves). A new technique for the deposition of pre-chosen amounts of copper on a ruthenium surface was investigated; this technique and the results are presented in Chapter 4. We succeeded in combining the advantages of both metals (viz. the high activity of ruthenium and the catalytic stability of copper), in one catalyst. The performance of the bimetallic catalysts in the hydrogenation of benzene was investigated, and is described in Chapter 4 as well.

REFERENCES 1 K. Weissermel and H.J. Arpe, "Industrial Organic Chemistry", Verlag Chemie, New York, 1978. 2 R. Pearce and W.R. Patterson, "Catalysis and Chemical Processes", Leonard Hill, New York, 1981, p. 316. 3 C. van Moesdijk, Polytechnisch Tijdschrift, 36 (1981) 147. 4 0. Immel, H.H. Schwarz, K. Starke and W Swodenk, Chem. Ing. Tech., 56 (1984) 612. 5 J.A. Don, Ph. D. Thesis, Delft, The Netherlands, (1981). 6 P.J. van der Steen, Ph. D. Thesis, Delft, The Netherlands, to be published. 7 J.W.A. Sachtler and G.A. Somorjai, J. Catal., 89 (1984) 35. 8 C. Kordulis, A. Lycourghiotis and S. Voliotis, Appl. Catal., 11 (1985) 301. 9 H.D. Lanh, H.S. Thoang, H. Lieske and J. Vlter, Appl. Catal., 11 (1984) 155. 10 J.P.G. Kehoe and J.B. Butt, J. Appl. Chem. Biotechnol., 22 (1972) 23. 11 R.Z.C. van Meerten and J.W.E. Coenen, J. Catal., 37 (1975) 37.

12 J.K. Marangozis, B.G. Mantzouranis and A.N. Sophos, Ind. Eng. Chem. Prod. Res. Dev., 18 (1979) 6 1 . 13 F. J i r a c e k , J . Pasek and J . Horak, A.I.Ch.E. J . , 15 (1969 100. 11 R. Badilla-Ohlbaum, H.J. Neuburg, W.F. Graydon and M.J. P h i l i p s , J . C a t a l . , 17 (1977) 273. 15 K. Nakano, Y. Fueda, T. Uchino and K. Kusunoki, J. Chem. Eng. Jpn., 15 (1982) 397. 16 K.H.V. Prasad, K.B.S. Prasad, M.M. Mallikarkunan and R. Vaidyeswaran, J. Catal., 81 (1981) 65. 17 L.M. Mamaladze, N.V. Nekrasov, B.S. Gudkov and S.L. Kiperman, Aota. Chim. Acad. Sci. Hung., 92 (1977) 73. 18 G.I. Jenkins and E. Rideal, J. Chem. Soc, vol. 3 (1955) 2196. 19 P. Tetenyi and Z. Paal, Z. Phys. Chem. (Neue Folge), 80 (1972) 63. 20 J.J. Rooney, Chem. Britain, 2 (1966) 212.

5
C H A P T E R 2

GAS-PHASE HYDROGENATION OF BENZENE OVER RUTHENIUM-ON-SILICA by

*)

M.C. Schoenmaker-Stolk, J.W. Verwijs, J.A. Don and J . J . F . Scholten Department of Chemical Technology, Delft U n i v e r s i t y of Technology, J u l i a n a l a a n 136, 2628 BL D e l f t , The Netherlands.

ABSTRACT A study i s made of the gas-phase hydrogenation of benzene over a r u t h e n i u m - o n - s i l i c a c a t a l y s t in t h e temperature range from 300 to 415 K and a t a t o t a l p r e s s u r e of 130 kPa. The t e x t u r e of the c a t a l y s t i s s t u d i e d by TEM, p h y s i s o r p t i o n of n i t r o g e n , chemisorption of hydrogen and by mercury p e n e t r a t i o n . Surface a n a l y s i s i s performed by XPS/AES. The a d s o r p t i o n e n t h a l p i e s of t h e r e a c t i o n determined. On the b a s i s of the k i n e t i c s , a r e a c t i o n mechanism i s proposed in which the r a t e - d e t e r m i n i n g s t e p s h i f t s from t h e f i r s t hydrogen a d d i t i o n t o benzene a t low t e m p e r a t u r e s t o t h e hydrogen a d d i t i o n t o cyclohexene a t higher temperatures. An approximate diagram i s c o n s t r u c t e d r e p r e s e n t i n g t h e change of t h e free e n t h a l p y as a function of the e x t e n s i o n of t h e r e a c t i o n . intermediates 1,4-cyclohexadiene and cyclohexene and of cyclohexane on ruthenium a r e

Paper accepted for p u b l i c a t i o n in Applied C a t a l y s i s .

6
2.1 INTRODUCTION It is well known that the gas-phase hydrogenation of benzene in the ' absence of catalysts is impossible, at least at temperatures below the dissociation temperature of hydrogen, and the same is true for the hydrogenation of cyclohexene and of the two cyclohexadiene isomers. However, the catalytic hydrogenation, first reported by Sabatier in 1901 [1] proceeds under relatively mild conditions over many metals [2]. The catalytic activities of several metals are summarised in the discussion of Chapter 3 of this thesis, in the form of a Tanaka-Tamaru plot [3]. Less is known about the behaviour of ruthenium as a catalyst. Kubicka [4] reports superior activity of ruthenium on silica, as compared with other metals. Don and Scholten [5], working with nonsupported ruthenium at ambient temperatures and pressures, found very high hydrogenation activities as . compared with platinum, provided the surface is free of impurities like oxygen and chlorine. Under these conditions the catalyst stability is very limited however, total deactivation occurring in periods of about 12 hrs in the presence of water in the feed. Van der Steen and Scholten [6] used highly purified ruthenium powders, as evidenced by XPS analysis. In this case the lifetime of the catalyst was 6 hrs at the utmost. As to the kinetics of the reaction all investigators agree that at temperatures below about 400 K and at atmospheric pressure the reaction order in benzene is near zero and in hydrogen in between 0.5 and 1.0 [7-9]. Such kinetics are found with practically all other metals. In this article we report on the kinetics of the reaction over a 0.4 wt$ Ru-on-silica catalyst in the temperature range from 300 to 400 K. Also the texture of the catalyst will be discussed extensively. Finally, we will reflect on the reaction mechanism on the basis of the gradual change of the standard free enthalpy of the reactants, reaction intermediates and products as a function of the extension of the reaction.

7
2 . 2 EXPERIMENTAL

2.2.1 M a t e r i a l s Benzene, "ftlr die S p e c t r o s c o p i e " , as well as cyclohexene, were obtained from Merck, FRG. 1,4-Cyclohexadiene ( p u r i t y 97%) was s u p p l i e d by Aldrich Chemie, Belgium. Drying and f u r t h e r d e s u l p h u r i z a t i o n of t h e s e r e a c t a n t s were performed by adding an excess of "Drina", a 9:1 Pb/Na a l l o y from Merck, followed by d i s t i l l a t i o n in an u l t r a - p u r e Pyrex g l a s s a p p a r a t u s under oxygen-free n i t r o g e n as a s h e l t e r g a s . Sulphur being a s t r o n g poison in c a t a l y t i c benzene hydrogenation, the benzene p r e t r e a t m e n t was extended by s l u r r y ing with 4 g.dm of reduced Ru 2 -1 powder, with S(BET)=6 m .g , under dry, oxygen-free n i t r o g e n for 30 min. Hydrogen, from Hoek-Loos, The N e t h e r l a n d s , was f u r t h e r p u r i f i e d as i n d i c a t e d in t h e s e c t i o n d e s c r i b i n g the flow a p p a r a t u s . The c a t a l y s t support was s i l i c a , s p h e r i c a l , from S h e l l , type CLA 33569C. According t o the 2 -1 manufacturer S(BET)=130 m .g . and t h e average pore diameter i s 53 nm. This m a t e r i a l was crushed t o p a r t i c l e s with minimum s i z e 0.85 m m and maximum s i z e 1.7 mm. Ruthenium t r i c h l o r i d e (spec pure) was supplied by D r i j f h o u t , Amsterdam. 2 . 2 . 2 C a t a l y s t c h a r a c t e r i z a t i o n and a d s o r p t i o n measurements The pore volume d i s t r i b u t i o n of the support was determined by mercury p e n e t r a t i o n a t p r e s s u r e s up t o 200 MPa, applying a Poroslmeter, type 2000, from Carlo Erba, Italy. Volumetric a d s o r p t i o n measurements of N_, H_ and cyclohexene were c a r r i e d out in a "micro-BET-apparatus" provided with a Baratron p r e s s u r e gauge (MKS Instruments I n c . , Burlington, Mass., USA) equipped with s i n g l e sided
sensors.

The BET s u r f a c e a r e a was c a l c u l a t e d from the N_ a d s o r p t i o n isotherm a t ^ 2 78 K, t a k i n g for the c r o s s - s e c t i o n a l a r e a of a n i t r o g e n molecule 0.162 nm . The f r e e - m e t a l surface a r e a was c a l c u l a t e d from the e x t e n t of s t r o n g H chemisorption a t 295 K. On the analogy of Anderson's r e c i p e for the case of platinum [ 1 0 ] , t h e t r a n s i t i o n point between s t r o n g and weak chemisorption was a r b i t r a r i l y taken a t 133.23 Pa. The number of ruthenium s u r f a c e atoms 19 2' was assumed t o be 1.63x10 per m , and t h e s u r f a c e s t o i c h i o m e t r y was assumed t o correspond t o one H atom per s u r f a c e Ru atom.

8 Adsorption measurements of cyclohexene were c a r r i e d out in a "micro-BETa p p a r a t u s " , which for t h i s s p e c i a l occasion had been provided with a s i d e tube with stopcock connected t o the apparatus and f i l l e d with cyclohexene, cooled down t o 78 K. Dosing of cyclohexene was performed by opening the stopcock and removing the Dewar cooling v e s s e l for a s h o r t t i m e . For every isothermal measuring point an e q u i l i b r i u m time of 20 min was t a k e n . The i s o s t e r i c enthalpy of a d s o r p t i o n was c a l c u l a t e d from the Clausius-Clapeyron equation. Surface a n a l y s i s was c a r r i e d out in a Leybold-Heraeus (FRG), type LHS-10 XPS/AES a p p a r a t u s . A MgKa e x c i t a t i o n source (energy 1253.6 eV) was applied a t the o p e r a t i n g c o n d i t i o n s of 1 3 kV and 20 mA. S p e c t r a l l i n e s were compared with standard values [ 1 1 ] . Samples were p r e t r e a t e d in vacuo or prereduced a t 670 K in a 90? Ar + 10$ H mixture in a p r e p a r a t i o n chamber connected t o the XPS/AES chamber via a v a l v e l e s s U H V lock. Electron micrographs of the reduced and p a s s i v a t e d c a t a l y s t were taken with a P h i l i p s E M U20T apparatus.The c a t a l y s t was mortared and embedded in a mixture of 70% methylmethacrylate and 30$ b u t y l m e t h a c r y l a t e . After c u r i n g a 70 nm t h i c k s l i c e was cut with an u l t r a microtome ( U l t r a c u t E, R e i c h e r t ) with a diamond c u t t e r . The enthalpy of a d s o r p t i o n of 1,4-cyclohexadiene being unknown in t h e l i t e r a t u r e , we decided t o e s t i m a t e i t s value by performing a TPD measurement of t h i s compound adsorbed on a "spec pure" ruthenium sample, type P u r a t r o n , from Johnson and Matthey, London. The method of measurement i s analogous to t h a t described by Konvalinka and Scholten [12] for t h e case of nond i s s o c i a t i v e a d s o r p t i o n with simultaneous r e a d s o r p t i o n . 2 . 2 . 3 Hydrogenatlon equipment For determining t h e performance of the c a t a l y s t , s e e F i g . 1, the numbers (1) t o (11) i n c l u s i v e , a continuous flow equipment with a fixed-bed r e a c t o r was used, o p e r a t i n g in the p r e s s u r e range from 0.1 t o 0.5 MPa. Oxygen was removed from the hydrogen gas by l e a d i n g i t over a Pd/AlpO. c a t a l y s t (BASF FRG, type R - 0 - 2 0 H D , and helium was p u r i f i e d from oxygen by leading i t over f i n e l y d i s p e r s e d copper on s i l i c a (BASF FRG,type R - 3 - 1 1 1 ) ( 2 ) . Both gases were dried over molecular s i e v e s , type 3A ( 3 ) . The gas flows were r e g u l a t e d by mass flow c o n t r o l l e r s , type F-201, from Inacom Instruments ( 4 ) . Benzene, and a l s o cyclohexene and 1 .M-cyclohexadiene, was evaporated by

9 leading f i n e l y divided hydrogen or helium through the l i q u i d , which was s t o r e d in a s t a i n l e s s - s t e e l v e s s e l (5) provided with a - h e a t i n g j a c k e t through which t h e r m o s t a t t e d water was c i r c u l a t e d . The p a r t i a l benzene p r e s s u r e was a d j u s t e d by r e g u l a t i n g the space v e l o c i t y of the c a r r i e r gas and t h e t e m p e r a t u r e of the l i q u i d .

FIGURE 1 Continuous-flow fixed-bed hydrogenation equipment. For explanation see numbers i n the t e x t . After p a s s i n g the evaporator (5) t h e gas mixture was led via heated tubes t o t h e r e a c t o r ( 6 ) . The r e a c t o r was a s t a i n l e s s - s t e e l tube with an i n s i d e diameter of 10 m m and a length of 40 mm. The c a t a l y s t was fixed in t h e r e a c t o r in between two s t a i n l e s s - s t e e l g r i d s . Temperatures up t o 7.70 K could be r e a l i s e d by an oven put around the r e a c t o r . The temperature was kept c o n s t a n t by means of a Eurotherm t h y r i s t o r c o n t r o l l e r t o within 0.5 K. The product gas mixture flowed through heated tubes t o t h e gas chromatograph ( 7 ) . Samples were taken a u t o m a t i c a l l y by a pneumatically a c t u a t e d Carle valve ( 8 ) . They were l e d through a 4 m long column of s t a i n l e s s s t e e l diameter 3 mm) f i l l e d with 30$ 1 , 2 , 3 - t r i s ( 2 - c y a n o e t h o x y ) p r o p a n e on Chromosorb W-HP, 80-100 mesh. The column temperature was kept a t 335 K. The samples were analysed by a flame i o n i s a t i o n d e t e c t o r , coupled t o a Hewlett Packard 5704A e l e c t r o m e t e r . The peak a r e a s were recorded and i n t e g r a t e d by a microprocessor ( D i g i t a l LCI 1 1 / 0 3 ) . (inner

10

The product gas was led through a heated back p r e s s u r e - r e g u l a t o r ( 9 ) , a Hersch c e l l ( 1 0 ) , in order t o determine the oxygen content [ 1 3 ] , and through a water-cooled condenser ( 1 1 ) . F i n a l l y , t h e gas was vented t o t h e atmosphere. 2 . 2 . 1 C a t a l y s t p r e p a r a t i o n and c h a r a c t e r i z a t i o n The c a t a l y s t was prepared by the i n c i p i e n t wetness method [ I t ] . A 0 . 0 6 M s o l u t i o n of ruthenium t r i c h l o r i d e in 1 M HC1 was dropped slowly into a v e s s e l c o n t a i n i n g the p r e - d r i e d support m a t e r i a l , which was r e g u l a r l y s t i r r e d . The maximum volume of l i q u i d was determined beforehand by measuring t h e amount of water needed t o a r r i v e a t the "caking p o i n t " . Next, the sample was d r i e d in a i r a t 100 K for 17 h r s . Reduction was performed in hydrogen (60 cm (STP).min ) a t 673 K for 3 h r s . The f i n a l r e d u c t i o n temperature was . The c a t a l y s t was cooled down t o room reached a t a r a t e of 0.5 K.min

temperature under hydrogen and f i n a l l y hydrogen was slowly r e p l a c e d by a i r , by which the metal surface was p a s s i v a t e d .

50

number of particles 25
{%)

0 0 1.25 2.5 3.75 5.0 6.25 particle diameter (nm)

FIGURE 2 Histogram giving the Ru p a r t i c l e diameter d i s t r i b u t i o n , from EM micrographs.

11

From I n d u c t i v e Coupled Plasma spectrometry (Jobin Yvon, type JY 38 a p p a r a t u s ) a ruthenium content of 0.4 wt? was found. I n s p e c t i o n of the e l e c t r o n micrographs showed the ruthenium p a r t i c l e s to be homogeneously d i s t r i b u t e d over the support. Broken c a t a l y s t particles showed the c a t a l y s t not t o have a mantle c h a r a c t e r , but a homogeneous metal p a r t i c l e d i s t r i b u t i o n . A sample of about 300 metal p a r t i c l e s in a photograph with a m a g n i f i c a t i o n f a c t o r of 120,000, yielded the s i z e histogram presented in F i g . 2. From t h i s f i g u r e a volume-surface mean p a r t i c l e diameter of 2.7 nm was c a l c u l a t e d from:
5
= 5 =

EM

VS

? V di ' K X 4

(1)

As the number of particles counted is very low, d_.. gives only a rough indication of the mean particle size. 2 -1 From hydrogen chemisorption a free ruthenium surface area, S, of 100 m .g
n

Ru was arrived at. Assuming the metal to be totally accessible to hydrogen and the ruthenium particles to be spheres, the mean particle diameter follows from:

dH dvs - kJLS
S

(2)

in which V i s t h e metal volume per gram of ruthenium. I t t u r n s out t h a t d _ H is 4.9 nm. Comparing this value with the d, value of 2.7 nm, it follows that S in equation (2) is about 55? of the total metal surface area. Hence the fraction of metal area strongly fixed to the silica support may be of the order of 45$ of the total metal area, and/or this percentage of the ruthenium surface area is poisoned and not accessible to hydrogen. XPS/AES analysis of the catalyst is represented in Fig. 3. Carbon, the main trace impurity, probably stems from the ruthenium, as it was not detected on the bare support. However, the spectrograms recorded do not show directly whether the carbon is located on the metal particles or on the support material. The absence of chlorine on the surface is remarkable, considering the high amounts of this element detected on ruthenium powder samples [5].

12

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oo

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oo CL o.

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55-^55 ^ J
^ ^ < m on ai \ + / cc cc o cc et: z 260 k. energy eV 520 780 1040

1300

FIGURE 3 XPS/AES spectrogram of 0.H wt? R u - o n - s i l i c a .


2 The BET surface area of the catalyst was 115 m .g -1 , in fair agreement

with the support area provided by the manufacturer. This points to the absence of any detrimental action on the support during catalyst preparation. From mercury penetration, a pore volume distribution curve (dV/dr as a function of r) resulted, with a sharp maximum at a pore radius of 25 nm, in good accordance with the value of 26 nm mentioned by the manufacturer. The 3 -1 total pore volume from mercury penetration was 0.72 cm .g (manufacturer: 3 _1 0.85 c m . g ) . .

13

2.3 RESULTS

2.3.1 Adsorption measurements For the construction of a plot of the change of free enthalpy in the course of the c a t a l y t i c reaction from benzene to cyclohexane, the enthalpies of adsorption of the reactants, the intermediates and the products are needed. These values are discussed in the f i r s t part of this section. The mode of adsorption of benzene on several transition metals i s well documented [15-17], and i t s strength i s influenced by the degree of electron filling of the d - o r b i t a l s . For the case of ruthenium we select, as a f i r s t approximation, the enthalpy value given by van Meerten c . s . [18] for the case of nickel-on-silica, the number of d-electrons in ruthenium being very close to that in nickel, viz. 15 and 16 respectively. W e then arrive at an approximate value of -59 kj.mol The TPD profile of 1,^-cyclohexadiene, measured according to Ref. [12] in an excess of argon as a shelter gas, shows two peaks, viz. a small peak at 313 K and a larger one at 533 K. Applying the TPD equation for f i r s t order

2 volume adsorbed (molecules CgH-iQ x108.m~2Ru) 1

0 0
P

0.5
C6HlO(kPQ)

1.0

FIGURE U Reversible part of the adsorption isotherms of cyclohexene on ruthenium powder.

14

desorption with simultaneous readsorption [12], and assuming the entropy of the adsorbed molecules to be zero, an adsorption enthalpy of -122 kj.mol was calculated for the weakly adsorbed part. The enthalpy of adsorption of the strongly held part is of the order of -198 kJ.mol~ . The reason for the existence of the strongly held 1,4-cyclohexadiene i s unknown; we suggest that some polymerization of this compound occurs, but this requires further research.
Fig. 4 presents the adsorption isotherms of cyclohexene on ruthenium powder, prepared by reduction of RuO after calcining at 1470 K as described by J.A. Don c.s., their sample B in Table 1 [19]. Part of the cyclohexene appeared to disproportionate on ruthenium into benzene and hydrogen. This corresponds to about 30? of the amount totally adsorbed. This type of destructive adsorption is not included in the isotherms; only the reversible parts adsorbed at 294 K and 337 K are plotted. From the Clausius-Clapeyron equation the following adsorption enthalpies are calculated: at 6=0.05, -AH . =26.5 kj.mol"1 ; at 6=0.1, -AH.. =37.2 kJ.mol"1 ; at 6=0.25, ads , ads

-AH _ , =44.2 kJ.mol ..Hence an indication i s found of an increasing enthalpy ads of adsorption with increasing coverage. This might be due to an increasing l a t e r a l interaction of cyclohexene molecules with increasing coverage. In the l i t e r a t u r e no values are to be found for the enthalpy of adsorption of cyclohexane on ruthenium. For the time being we adopt as a f i r s t approximation the enthalpy of adsorption of cyclohexane on activated carbon of 34 kJ.mol , as tabulated by Walker, for the case of low coverage [20], in view of the metallic character of carbon. 2.3.2 Kinetics of the hydrogenatlon of benzene, 1,4-cyclohexadiene and cyclohexene With ruthenium as a catalyst kinetic measurements are hampered by a decreasing activity ( i n s t a b i l i t y ) caused by the gradual deposition of by products like cyclohexyl- and 1,4-dicyclohexylcyclohexane [ 6 ] . In Fig. 5 the change of catalytic a c t i v i t y as a function of time i s plotted for experiments at respectively 303 and 400 K under the experimental conditions indicated in the legend of the figure.

15

48 40 32

I <

I
-

24' TON (molecules C5H5 i x10 3 .site" 1 . 16 s-1) 8 0


l I l

400 K -

^o___^^^303 K
I I I I

720

1440

2160

reaction time (min)

Figure 5. The change of the rate of benzene conversion over 0.4 wt% Ru-onsilica as a function of time at: total pressure 110 kPa, hydrogen pressure 40 kPa, benzene pressure 2 kPa and space velocity 3 - 2 2Ru.F - 1 ' 3 5x103 cm3 (STP).m" 5x10 cm (STP).m Ru.h . The oxygen content in the product gas stream was 4 ppm. The low stability of the catalyst at 303 K is in accordance with the results of Don and Scholten [5] and of van der Steen and Scholten [6]. Interestingly, at 100 K a very stable behaviour is observed. This, we think, is related to the lower coverages of benzene and of cyclohexene during reaction at this higher temperature, as a result of which the rate of alkylation of benzene by cyclohexene is appreciably lower. Moreover, the alkylatlon products, if present, will desorb much faster at 100 K than at 303 K. The reaction orders are determined from the curves represented in Fig. 6a and Fig. 6b. At 303 K the rate of hydrogenation appeared to be zero order in the pressure of benzene, whereas the order in hydrogen is 1.2.

16

-1.5 -2.0
In TON _25

(molecules C5H5. site" 1 .s" 1 ) -3.0 -3.5

-4.0
0

0.5
lnP

1.0

1.5

2.0

2.5

C6H6(kP)

Figure 6

- 2 - 3 In TON (molecules CgHg. site" 1 , s"1 ) - 5 - 6 - 7 2.5 _


4

3.0

3.5

4.0

4.5

In P H 2 (kPa) Figure 6 FIGURE 6 Benzene (a) and hydrogen p r e s s u r e dependence (b) of the benzene hydrogenatlon r a t e .

17
Experimental conditions are indicated in Table 1..Surprisingly, at 100 K a strongly deviating pressure dependence was found, especially with respect to the order in hydrogen, which increased from 1.2 (303 K) to 2.0 (400 K ) . In calculating the results (Table 1) we took into account the following factors: a) the measurements were performed at differential reactor conditions, the benzene conversion being below 10$; b) every point was measured in triplicate and, when necessary, corrections were made for deactivation. TABLE 1 Reaction orders in the hydrogenation of benzene over 0.4 wt$ Ru-onsilica. Total pressure 130 kPa and space velocity l ) 3 _ 2 - i 2x10 cm (STP).m Ru.h . Total pressure is reached in each case by adding helium.

Temperature (K)

order in benzene

order in hydrogen

303 400

0.0 0.2

1.2

(b)

2 . 0 (b)

a) within the range of benzene pressures from 1.9 - 7.9 kPa and at a hydrogen pressure of 79 kPa. b) within the range of hydrogen pressures from 1 3 - 8 9 kPa and at a benzene pressure of 5 kPa. Apparent activation energies were calculated from measurements carried out under the conditions indicated in the legend of Fig. 7. In calculating the reaction rate constant, a linear increase of the reaction orders with increasing temperature i s assumed (as was found by van Meerten c . s . for reactions over a nickel catalyst [ 9 ] ) . In the figure the apparent activation energies in kJ.mol at various temperature levels are indicated between brackets. The curious change of the apparent activation energy as a function of temperature, and especially the negative values of t h i s quantity found above 355 K, were also observed by Kubicka [4] for ruthenium-on-silica catalysts. W e return to t h i s in the discussion.

18

Temperature {K) - 8 In k (molecules CgHg. site~\s .divided - I Q byfPc 6 H 6 l a ^PH 2 ] P ) -11 416 385 357 333 313

2.4

2.6

2.8

3.0

3.2

1000/T (K~1)
FIGURE 7 Arrhenius plot of the r a t e of hydrogenation of benzene over 0.4 wt$ R u - o n - s i l i c a . Total pressure 130 kPa, hydrogen p r e s s u r e 63 kPa, benzene p r e s s u r e 6 kPa, helium p r e s s u r e 61 kPa and space v e l o c i t y 6x10 cm3(STP) .m~ 2 Ru.h _1 .

In t h e study of r e a c t i o n mechanisms i t i s often h e l p f u l t o I n v e s t i g a t e the k i n e t i c s of t h e presumed elementary r e a c t i o n s t e p s . Therefore, the hydrogenations of 1,4-cyclohexadiene and of cyclohexene were s t u d i e d s e p a r a t e l y . Though i t cannot be r u l e d out t h a t 1,3-cyclohexadiene i s a l s o involved in the mechanism as an i n t e r m e d i a t e , we l i m i t e d our study t o the 1,1-isomer, as t h i s isomer forms a very s t a b l e b i d e n t a t e s u r f a c e complex [21]. The r a t e of hydrogenation of 1,1-cyclohexadiene (see Table 2) was pressure. it

extremely high even a t room temperature and 130 kPa t o t a l

Therefore we did not succeed in measuring t h e r a t e of r e a c t i o n , but t u r n s out t o be 0.6 CgHg molecules per s i t e per second. Besides the

should be higher than the t o t a l conversion per u n i t time. The l a t t e r number

19 formation of cyclohexane, cyclohexene was observed as a hydrogenation by product, and, n o t w i t h s t a n d i n g the presence of an excess of hydrogen, a r e l a t i v e l y l a r g e amount of benzene was formed as w e l l . The fact t h a t both hydrogenation and dehydrogenation occurred w i l l s e r v e as a s t r o n g argument in the f i n a l d i s c u s s i o n of t h e mechanism. TABLE 2 Product gas composition in t h e hydrogenation of 1,4-cyclohexadiene

over 0.1 wt% R u - o n - s i l i c a . Total presure 130 kPa and 1) 3 -2 -1 space v e l o c i t y 9x10 cm (STP).m Ru.h . The t o t a l p r e s s u r e i s reached in each case by adding helium. P a r t i a l p r e s s u r e s of H_ pressure (kPa) 62.5 62.5 62.5 13.2 52.6 86.8 78.3 78.3 78.3 ^6^8 p r e s s u r e (kPa) 2.03 2.03 2.03 2.08 2.08 2.08 0.89 3.25 5.47 temperature (K) 305 358 392 400 400 400 400 400 400
C H

(a)

6 6 (kPa)

C H

6 10 (kPa)

C H

6 12 (kPa)

0.06 0.66 0.85 1.15 0.95 0.84 0.33 1.25 2.09

0.04 0.27 0.17 0.56 0.10 0.03 0.01 0.01 0.01

1.93 1.10 1 .01 0.37 1.03 1.21 0.55 1.99 3.37

a ) the p a r t i a l p r e s s u r e s i n t h e o f f - g a s a r e a measure of the amounts of CfiH8 converted i n t o C,H,, C.-H. Q and CgH per u n i t time.

Contrary t o the r e s u l t s found with 1 ,4-cyclohexadiene the main product observed i n the hydrogenation of cyclohexene was cyclohexane and only small amounts of benzene were d e t e c t e d . I t i s important t o n o t e here t h a t t h e r a t e of cyclohexene hydrogenation was found t o be always higher than t h a t of benzene under comparable c o n d i t i o n s . The r e s u l t s a r e summarized in Table 3 . Again the r e a c t i o n r a t e s were h i g h , so t h a t we a r e not f u l l y s u r e t h a t we measured f a r from e q u i l i b r i u m . Keeping t h i s in mind i t i s not p o s s i b l e t o present h e r e the p r e c i s e o r d e r s of t h e r e a c t i o n , but from Table 3 i t is

20
seen the reaction is likely to be first order in both the hydrogen and the cyclohexene pressure (compare lines 4, 5 and 6 in the Table for the order In hydrogen and lines 7, 8 and 9 for the order in cyclohexene). Such kinetic behaviour is to be expected as long as we are dealing with a low cyclohexene coverage. A first order relationship for hydrogen is less easy to understand, considering that the high partial hydrogen pressure leads to a high hydrogen coverage. This problem will be dealt with in the discussion. TABLE 3 Gas composition In the reactor exit, in the hydrogenation of cyclohexene over 0.1 wt$ Ru-on-silica. Total pressure 130 kPa and 1 ) a - 2 - 1 space velocity 6x10 cm (STP).m Ru.h . Total pressure is reached in each case by adding helium. Partial pressures of H2 pressure (kPa) 62.5 62.5 62.5 13.1 39.5 65.8 77.6 77.6 77.6 6 10 temperature pressure (kPa) (K) 6.25 6.25 6.25 7.18 7.18 7.18 1.97 3.42 5.67
C H

C,Hg (kPa) 0.01 0.05 0.14 0.01 0.01 0.01 0.01 0.01 0.01

C,H. _ (kPa) 6.19 5.07 4.75 1.42 4.46 6.81 1.95 3.34 5.49 converted

305 358 400 305 305 305 305 305 305

a) the partial pressures are a measure of the amount of CAi.Q into C,H, and CgH._ per unit time.

In Table 4 reaction rates for benzene and cyclohexene and their ratios are presented as a function of temperature. As said before, the distance from equilibrium is strongly influenced by the reaction temperature. In the case of benzene hydrogenation we are far from equilibrium, whereas in the case of cyclohexene this situation is never realised. Therefore, conclusions from Table 4 are of a qualitative nature

21

o n l y . I t i s found t h a t the r a t e s of r e a c t i o n run a n t i p a r a l l e l when t h e t e m p e r a t u r e i s I n c r e a s e d . An e x p l a n a t i o n of t h i s phenomenon and i t s consequences i s given in the d i s c u s s i o n . TABLE 4 Rate of cyclohexene and benzene hydrogenation and t h e i r r a t i o in the t e m p e r a t u r e range from 305 t o 410 K. Total p r e s s u r e 130 kPa, hydrogen pressure 62 kPa, benzene (cyclohexene) pressure 6 kPa, 4 3 -2 -1 helium pressure 62 kPa and space v e l o c i t y 6x10 cm (STP) .m Ru.h . , temperature (K) TON C,H, TON C 5 H 1 ( / a ; TONC6H10/TONC6H6 305 0.02 2.35 118 322 0.03 2.26 68 340 0.06 2.17 33 350 0.07 2.17 28 360 0.07 2.18 30 380 0.07 2.11 30 400 0.06 2.07 34 415 0.05

a) T0N=number of benzene (cyclohexene) molecules r e a c t e d per s i t e per second.

2.4 DISCUSSION For the heterogeneous c a t a l y t i c hydrogenation of benzene over group VIII m e t a l s , the following stepwise r e a c t i o n mechanism i s g e n e r a l l y adopted [22,23]: C 6 H 6 (g) H 2 (g) H 2 (g)
C H ( 6 10 S>

H 2 (g)

c 6

H 12

(g)

!!

II

tl

II

II

II
CVH (ads)

C 6 H 6 ( a d s ) + 2 H ( a d s ) z r C 6 Hg(ads)+2H(ads) ZZ

Cg^ Q (ads)+2H(ads) ^ r

The stepwise mechanism is based on, among other things, the often quoted [4,6,23] observation that the intermediate cyclohexene can desorb before further catalytic hydrogenation; this has never been observed for the cyclohexadienes. Apparently the cyclohexadienes are too strongly adsorbed to desorb before further hydrogenation. Derbentsev, Paal and Tetenyi [24] and Tetenyi and Paal [25] studied the reaction mechanism of benzene hydrogenation over several group VIII metals,

22
1H

ruthenium included. They started from nearly equimolecular mixtures of labeled benzene and unlabeled 1,3-cyclohexadiene and found that the radioactivity in the C,H.

product fraction was smaller than in the C,H 1 2

product fraction. This was explained by the introduction of a direct full hydrogenation of the adsorbed C,Hg ring in one step, besides the stepwise mechanism. Their conclusion is questionable in the light of our observation (see section Results and Table 2) that CfiHg is so strongly adsorbed that the CgHg coverage is extremely lowered. Starting from this high CgHg coverage, both C 6 H 6 and a CgH. /C.-H.. _ mixture are formed, at a rate which is about a hundred times as high as the hydrogenation rate of benzene. Table 2, line 4, shows that under certain reaction conditions more CgH. Q than CgH- 2 is formed from CfiHo. Therefore, we think the difference between radioactivity in the product fractions of CgH.- and CgH._ as observed by Derbentsev c.s. and by Tetenyi c.s. can be explained without the introduction of a direct full hydrogenation step of the C,H, ring. Moreover, the chances that adsorbed benzene reacts with 6 adsorbed hydrogen atoms, forming a CgH- 2 transition state in one step, should be low. We now first discuss the modes of binding of hydrogen on transition metal surfaces. From a survey article [26] it appears that there are at least five types of adsorbed hydrogen, their populations and adsorption enthalpies being measurable especially by means of the TPD technique. In general the absolute value of the adsorption enthalpies, AH . , range from values as low a -1 -1 as 36 kJ.mol up to values as high as 170 kJ.mol , and in this respect the

difference between the various transition metals seems to be marginal [26], The answer to the question which type of hydrogen is involved in a catalytic reaction depends on the temperature chosen. The value of -AH . /RT is indicative in this respect; a low absolute value of this quantity means that the rate of surface migration of hydrogen is high,and the same is the case for the rate of hydrogen desorption. Also the catalytic reactivity of hydrogen will be higher according as the -AH . /RT value is lower. Hence, in

the construction of a diagram of the free enthalpy of the reaction around room temperature (see Fig. 8 ) , an enthalpy of hydrogen adsorption has to be chosen corresponding to weakly adsorbed hydrogen. A generally accepted value for -AH (weakly bound hydrogen) is about 40 kJ.mol" [26].

23

60 40 20 0 - 20 - 40 - 60 (kJ.mol-1, - 8 0 -100 -120


/

I C 6 H 8 *2H 2
\

/C6H8(Q\

6 H 6 + 3 H 2'

. :' /in

. \ .\ : \ H2 (21'. \C6H10*
\' .

-C6H6(Q)/

+ 6H(n)

\ C 6 H 10 (a)\; 2 H ( a ) \\ '

13)'- \ i

\
_

|C 6 H12 C 6 Hi 2 (a)
l

100 extension of the reaction (%)

FIGURE 8 An approximate diagram of the change of the s t a n d a r d r e a c t i o n free e n t h a l p y in the hydrogenation of benzene as a f u n c t i o n of t h e e x t e n s i o n of the r e a c t i o n , for t h e case of the s t e p w i s e mechanism. For the hydrogen/benzene mixture in the g a s - p h a s e , AG i s taken zero as a r e f e r e n c e p o i n t . Upper l e v e l s : gas-phase h y d r o g e n a t i o n . Lower l e v e l s : c a t a l y t i c hydrogenation over ruthenium. Dashed l i n e s : extremely high a c t i v a t i o n e n e r g i e s . Dotted l i n e s : unknown but low a c t i v a t i o n e n e r g i e s . Temperature around 300 K. The free e n t h a l p y l e v e l s of C 6 H(ads), C,H g (ads) and CgH Included in t h i s diagram. (ads) a r e not

21

Around 300 K we observed a benzene hydrogenation r a t e which i s f i r s t order in hydrogen pressure. Inspection of hydrogen adsorption isotherms for the weakly bound types of hydrogen (see for instance Fig. 8 in Ref. [26]) shows the coverage to be nearly f i r s t order in hydrogen pressure. Hence we conclude that, notwithstanding the fact that the sum of the coverages of the strongly bound types of hydrogen equals unity, a weak hydrogen adsorption is present, causing the r a t e of benzene hydrogenation t o be f i r s t order. In the l i t e r a t u r e this type of hydrogen is often called "hydrogen in excess of the strongly held monolayer" [26]. Our conclusion i s in accordance with the results of Aben c . s . [27] for the case of benzene hydrogenation over platinum. These authors observed a r a t e , around room temperature, which is f i r s t order in the population of the hydrogen TPD peak representing weakly chemisorbed hydrogen. In Fig. 8 we present a reaction free enthalpy diagram in which the reaction free enthalpies of the various reaction steps are plotted as a function of the extension of the reaction. The virtual free enthalpy values for the non c a t a l y t i c hydrogenation are taken from Janz [ 2 8 ] . Starting from t h i s , the free enthalpies of the surface reaction over ruthenium are calculated by subtracting from the gas-phase free enthalpy values the adsorption enthalpies given In the section Results. In the calculation of AG values, s t a r t i n g from A H values, the following approximate differential entropy values are introduced: [26] ASads . = -120 J.mol .K" hydrogen [18] ASads . = -110 J.mol .K~ benzene [28] 1, 1-cyclohexadiene AS . = -285 J.mol .K" cyclohexene cyclohexane AS . = -100 J.mol ads AS . = -100 J.mol
.K" .K"

The differential entropies chosen for cyclohexene and cyclohexane are rough estimates based on the fact t h a t , whereas the gas-phase entropies of these substances are nearly equal to that of benzene, the surface mobility of these molecules i s higher due to their lower enthalpies of adsorption. Fig. 8 demonstrates that the CgHgCads) level i s about 11 kJ.mol higher than the C,H,(ads) level. It follows that the free enthalpy of activation for step (1) to the right should be at least equal to t h a t value. The fact that the reaction can proceed, notwithstanding the thermodynamically

25
unfavourable high C,HD(ads) level, can be explained as follows. The rate of o C,H hydrogenation (step(2)) was found to be much faster than the rate of C,H, hydrogenation (step(D). Hence the population of the C,Hfi(ads) level is continuously depleted by the very fast reaction step (2). This means that the production of CfiHft(ads) continues, notwithstanding the unfavourable thermodynamic situation of an increase of AG for step (1) to the right.

Furthermore, the rate of reaction of step (1) to the right is Increased by the relatively high initial pressures of CgH, and H-, and their respective populations on the surface. The kinetic situation described above has recently been theoretically treated by Boudart [29]. In his terminology the stimulation of step (1) by pressure is called "pumping up", and the depletion of the C,H(ads) level by step (2) "pumping down" of the C,H(ads) concentration. The high rates we observed for step (2) and (3) point to step (1) being rate determining around 300 K. If this is correct, the observation that the total reaction around this temperature is zero order in the pressure of benzene can be explained from the fact that at room temperature C,H, coverage equals unity. We believe CfiH, to form a chemisorbed layer over the small chemisorbed hydrogen atoms bound in the holes in the ruthenium surface (for instance at the so called C Q sites [26]).

8
Our observation that during C,H hydrogenation both C,H, and a C,H /C,H
?

mixture are formed can be explained from the fact that (see Fig. above the C,H, level and 38 kJ.mol

8) the CgHg level is about 41 kj.mol

above the C,H.- level. The extremely high rates of these reactions, even at room temperature, indicate that the activation energy barriers between the C,Hg(ads) level and the C,-H,(ads) level, and between the CgHg(ads) level and the CfiH1f)(ads) level, are very low. At 300 K, where it is likely that the addition of hydrogen to benzene, step (1), is rate determining, we calculated from the Arrhenius plot (Fig. 7) an apparent activation energy of 3.8 kj.mol . By contrast, Kubicka [4]

reports in the same range of temperatures the much higher apparent activation energy of 30 kJ.mol . However Kubicka plotted the logarithm of

the reaction rate instead of the logarithm of the reaction rate constant as a function of the reciprocal temperature. If we adopt the same procedure we

26

a r r i v e a t an apparent a c t i v a t i o n energy of 38 kj.mol accordance with Kubikcka's v a l u e .

, in q u i t e good

In our work the most s t r i k i n g o b s e r v a t i o n i s the f a c t t h a t a t temperatures around 330 K the apparent a c t i v a t i o n energy r e a c h e s a n e g a t i v e v a l u e . In Kubicka's work the same phenomenon i s observed, and with o t h e r group VIII metals i t a l s o occurs (van Meerten c . s . [ 9 ] ) . The change i n t h e sign of the apparent a c t i v a t i o n energy i s accompanied by a dramatic change i n the r e a c t i o n o r d e r s of benzene and, e s p e c i a l l y , of hydrogen. We s p e c u l a t e t h i s t o be due t o a s h i f t of the r a t e determining s t e p from s t e p (1) t o s t e p ( 3 ) . This view i s supported by the f a c t that cyclohexene i s very weakly chemisorbed, so t h a t i t s coverage i s s t r o n g l y lowered a t higher t e m p e r a t u r e s . This in t u r n means t h a t the r a t e of s t e p (3) i s appreciably lowered. At the same time however, going from 300 K t o 400 K, t h e r a t e of s t e p (1) t o the r i g h t i s very s t r o n g l y i n c r e a s e d . Our view i s i l l u s t r a t e d by t h e a n t i p a r a l l e l change of TON C,H, and TON C,H,_ as can be
DO
D IU

seen from Table 4. As soon as the l a s t hydrogenation s t e p ( s t e p (3)) has become r a t e determining, we a r e d e a l i n g with t h e s i t u a t i o n t h a t t h i s s t e p i s preceded by two equilibrium r e a c t i o n s , s t e p (1) and s t e p ( 2 ) . The e q u i l i b r i u m c o n s t a n t s of s t e p (1) and (2) a r e given by, r e s p e c t i v e l y :
6

C6H8(a)
X S

(3)

1
and

" ~a
9

C6H6(a)

H(a)

C6H10(a)
x

(4)

C6H8(a)

2 9 H(a)

2 In both equations 6 , . is proportional to the hydrogen pressure. It ma; follows that in the overall rate equation the maximum value of the order in hydrogen will finally become 3. The same explanation and conclusion were arrived at by van Meerten c.s. [9], who, at the highest temperatures investigated by them, observed an order in hydrogen of 3 in the case of

27

n i c k e l . We, however, a r r i v e d a t an order of 2 in hydrogen and hence one might expect t h a t on ruthenium a l s o , a t s t i l l higher t e m p e r a t u r e s , above 400 K, t h i s high order i n hydrogen w i l l be found. Proceeding from 303 t o 400 K t h e order in benzene changes from 0.0 t o 0 . 2 . This p o i n t s t o t h e benzene coverage slowly d e v i a t i n g from the o r i g i n a l f u l l coverage a t 303 K. We expect t h a t f u r t h e r i n c r e a s i n g temperatures w i l l f i n a l l y r e s u l t i n a f u r t h e r i n c r e a s e in t h e " o r d e r of benzene p r e s s u r e . We f i n a l l y have t o e x p l a i n t h e occurrence of an apparent n e g a t i v e a c t i v a t i o n energy in t h e t e m p e r a t u r e range above.330 K (see F i g . 7 ) . From our c a l c u l a t i o n s i t appears t h a t t h e A H values of the e q u i l i b r i a (1) and (2) are very small (and p o s i t i v e ) i n c o n t r a s t with t h e AC v a l u e s . I t t h a t r e a c t i o n s t e p s (1) and ( 2 ) , as e q u i l i b r i a preceding t h e r a t e determining s t e p ( 3 ) , cannot e x p l a i n the n e g a t i v e apparent a c t i v a t i o n energy. A b e t t e r e x p l a n a t i o n seems t o be the f o l l o w i n g . With i n c r e a s i n g temperature t h e coverages of C,H,(ads) and e s p e c i a l l y C,H (ads) decrease d r a s t i c a l l y , and t h i s w i l l have a r e t a r d i n g e f f e c t on t h e r e a c t i o n r a t e , which manifests i t s e l f in the form of an apparent n e g a t i v e a c t i v a t i o n energy. Or, t o put i t i n another way, t h e A H values of t h e e q u i l i b r i a : CgH 6 (gas) CgHgUds) -AHg1 -AH a2 (5) (6) follows

C 6 H 1Q (gas) ^ T CgH 1 0 (ads) and H. (gas) = 2 2H (ads)

-AH . a3

(7)

as e q u i l i b r i a preceding the r a t e - d e t e r m i n i n g s t e p , w i l l change the apparent a c t i v a t i o n energy in t h e following way:


E AH AH

=nn

*=K^ rsi

"

,i

" A H _ - 3AH ,

(8)

app. with

s t e p (3)

al

a2

a3

[AH + A H + 3AH , ] > AH* . ,-, al a2 a3 s t e p (3)

(9)

28
2.5 CONCLUSION The mechanism of benzene hydrogenation over group VIII metals is highly complicated. From the stepwise reaction mechanism, adopted by the present authors and presented at the start of the discussion, it is seen that we are dealing at least with nine elementary steps. If the elementary steps (1), (2) and (3) are further split up into reaction steps in which only one hydrogen atom is added to the cyclic nuclei, we are even dealing with twelve steps. Therefore it is obvious that for a full mechanistic and kinetic analysis more research is needed, especially by a more detailed study of the kinetics of the elementary steps as such. In Chapter 3 of this thesis we will report on the kinetics of the hydrogenation of benzene over copper-on-silica.

ACKNOWLEDGEMENTS We thank Mr. A.P. Pijpers and Mr. J. Cremers (Department of Physical Chemistry, Central Laboratories, DSM, Geleen, The Netherlands) for carrying out the XPS/AES measurements and for their skilful help with the interpretation of the spectra. Thanks are also due to Mr. A. Pijpers, from the same department, for the TEM study, and to Mr. P. van Oeffelt for carrying out the 1,4-cyclohexadiene TPD measurement. Mr. J. Teunisse and Mr. N. van Westen, both from Delft University of Technology, assisted in the study of the catalyst texture. The investigations were supported (partly) by The Netherlands Foundation for Chemical Research (SON) with financial aid from The Netherlands Organization for the Advancement of Pure Research (ZWO).

REFERENCES 1 P. Sabatier and J.B. Senderens, Compt. Rend., 132 (1901) 210. 2 G.A. Somorjai, "Chemistry in Two Dimensions: Surfaces", Cornell University Press, Ithaca-London, 1981. 3 K.I. Tanaka and K. Tamaru, J. Catal., 2 (1963) 366.

29 4 H. Kublcka, J . C a t a l . , 12 (1968) 223. 5 J.A. Don and J . J . F . S c h o l t e n , Faraday D i s c u s s . (Chem. S o c ) , 72 (1982) 1145. 6 P . J . v . d . Steen and J . J . F . Scholten, "Proceedings of the 8th I n t e r n a t i o n a l Congres on C a t a l y s i s " , B e r l i n , Verlag Weinheim, 1984, vol. I I , p.659. 7 W.F. Taylor and H.K. Staf f i n , J. Phys. Chem., 71 (1967) 331U. 8 K.J. oon and M.A. Vannice, J . C a t a l . , 82 (1983) 457. 9.R.Z.C. v . Meerten and J.W.E. Coenen, J . C a t a l . , 37 (1975) 37. 10 J.R. Anderson, " S t r u c t u r e of M e t a l l i c C a t a l y s t s " , Academic P r e s s , New York, 1975, p.296. 11 "Handbook of X-Ray Photoelectron Spectroscopy", Perkin-Elmer, Eden P r a i r i e s , Minn., 1979. 12 J.A. Konvalinka, J . J . F . Scholten and J . C . Rasser, J . C a t a l . , 48 (1977) 374. 13 A. Verdin, "Gas Analysis I n s t r u m e n t a t i o n " , McMillan, London, 1973, p . 1 9 9 . 14 Y.W. Chen, H.I. Wang and J . G . Goodwin J r . , J . C a t a l . , 83 (1983) 415. 15 P.W. Selwood, J . Am. Chem. S o c . , 79 (1957) 3346. 16 D.M. Haaland, Surf. S c i . , 102 (1981) 405. 17 J . S . Lehwald, H. Ibach and J . E . Demuth, Surf. S c i . , 78 (1978) 577. 18 R.Z.C. v . Meerten and J.W.E. Coenen, J . C a t a l . , 46 (1977) 13. 19 J.A. Don, A.P. P i j p e r s and J . J . F . Scholten, J . C a t a l . , 80 (1983) 296. 20 P.L. Walker J r . , "Chemistry and Physics of Carbon", M. Dekker I n c . , New York, 1970, v o l . 6, p . 9 0 . 21 A.J. Pearson, " M e t a l l o - o r g a n i c Chemistry", John Wiley and Sons, C h i c h e s t e r . 1985, p . 2 5 5 . 22 S. S i e g e l , "Advances in C a t a l y s i s " , ( P . P . Eley, H. Pines and P.B. Weisz, Eds.), Academic P r e s s , New York, 1966, p . 1 2 3 . 23 F. Hartog and P. Z w i e t e r i n g , J . C a t a l . , 2 (1963) 7 9 . 24 Y.I. Derbentsev, Z. Paal and P. Tetenyi, Z. Phys. Chem. Neue Folge, 80 (1972) 5 1 . 25 P. Tetenyi and Z. P a a l , Z. Phys. Chem. Neue Folge, 80 (1972) 6 3 . 26 J . J . F . S c h o l t e n , A.P. P i j p e r s and A.M.L. H u s t i n g s , C a t a l . Re v . - S c i . - E n g . , 27 (1985) 151.

30

27 P.C. Aben, H. v . d . Eyk and J.M. Oelderik, "Proceedings of t h e 5th I n t e r n a t i o n a l Congres on C a t a l y s i s " , Miami Beach, F l o r i d a , (J.W. Hightower, E d . ) , North Holland Publishing Company, Amsterdam, 1972, vol. 1 , p.717. 28 G.J. J a n z , J. Chem. Phys., 22 (195*4) 751. 29 M. Boudart, J. Phys. Chem., 87 (1983) 2786.

31

C H A P T E R

GAS-PHASE-HYDROGENATION OF BENZENE OVER COPPER-ON-SILICA *) by M.C. Schoenmaker-Stolk, J.W. Verwijs and J . J . F . Scholten Department of Chemical Technology, Delft U n i v e r s i t y of Technology, J u l i a n a l a a n 136, 2628 BL D e l f t , The N e t h e r l a n d s .

ABSTRACT A study has been made of the k i n e t i c s and mechanism of the gas-phase hydrogenation of benzene over, a c o p p e r - o n - s i l i c a c a t a l y s t in t h e temperature range from 300 t o '150 K and a t 130 t o 395 kPa t o t a l p r e s s u r e . Attention has been given a l s o t o the k i n e t i c s of the hydrogenation of the r e a c t i o n i n t e r m e d i a t e s 1,4-cyclohexadiene and cyclohexene. Two d i f f e r e n t c a t a l y s t s were prepared on Shell s i l i c a spheres as a s u p p o r t , one according t o the Dutch Patent No. 143.139 and t h e o t h e r according t o European Patent No. 0006313. Their t e x t u r e and a n a l y t i c a l composition were s t u d i e d by means of TEM, n i t r o g e n p h y s i s o r p t i o n and c a p i l l a r y c o n d e n s a t i o n , a d s o r p t i v e decomposition of n i t r o u s o x i d e , atomic absorption spectrometry and XPS/AES a n a l y s i s . The c a t a l y s t prepared a c c o r d i n g t o European Patent No. 0006313 had a high mechanical s t r e n g t h , a p e r f e c t chemical s t a b i l i t y and a high s i n t e r i n g r e s i s t a n c e . The mean.copper p a r t i c l e diameter was 5.5 nm. The o t h e r c a t a l y s t displayed poor mechanical s t r e n g t h and fragmented during t e s t i n g .

Paper accepted for p u b l i c a t i o n i n Aplied C a t a l y s i s .

32

A reaction mechanism is formulated on the analogy of the mechanism proposed for the hydrogenation of benzene over ruthenium (see Chapter 2 ) . The catalytic a c t i v i t y of copper i s compared with that of several other transition metals and presented in the form of a modified Tanaka-Tamaru plot.

3.1 INTRODUCTION Supported copper catalysts are used in several industrial processes, for instance in the dehydrogenation of the lower alcohols to the corresponding ketones and in the dehydrogenation of cyclohexanol to cyclohexanone and of nitrobenzene to aniline [1]. Furthermore, copper is applied as a catalyst in the water gas shift reaction, in the low pressure methanol synthesis and in the partial hydrogenation of fatty acids [2]. In the hydrogenation of benzene copper exhibits a poor catalytic activity [3.1*]; its activity around room temperature is a thousand times lower than that of nickel. The lower activity of copper Is partly due to its limited ability to chemisorb hydrogen. Mikovsky, Boudart and Taylor [5], working with copper foil, detected some hydrogen chemlsorption around 600 K. Pritchard et al. discovered that dissociative hydrogen chemisorption takes place on the high Miller index planes of copper only, the low index planes (100), (111) and (110) being inactive [6]. On Cu(311) these workers found a heat of chemisorption of 39.8 kJ.mol" whereas the activation energy of adsorption amounted to 21 kJ.mol In view of the above we thought it would be worthwhile to test small copper crystallites dispersed on a support as a benzene hydrogenation catalyst, the small crystallites in such a system having a high free-copper surface area and exposing a relatively large fraction of high index planes. On account of the low activity of copper it is necessary to choose a high reaction temperature, but then the difficulty is encountered that the temperature at which copper starts to sinter is relatively low. As a rule of thumb it can be stated that migration of copper atoms over the surface of copper starts at around 1/3 of the melting temperature of the metal, the so called Hilttlg temperature. It follows that just above 452 K the danger of sintering of copper exists already.

33 S i n t e r i n g of copper can be l a r g e l y prevented by anchoring the copper c r y s t a l l i t e s t o the s u r f a c e of a s u p p o r t . This can be achieved for example by the method described by Geus [7] in which copper i s p r e c i p i t a t e d on t h e surface of s i l i c a in t h e form of copper hydroxy s i l i c a t e . After c a l c i n i n g and r e d u c t i o n , small copper c r y s t a l l i t e s remain which a r e fixed t o t h e s i l i c a v i a two-dimensional copper s i l i c a t e l a y e r s . Provided a very pure type of s i l i c a ( v i r t u a l l y sodium-free) i s employed, a very high s i n t e r i n g r e s i s t a n c e of both copper and s i l i c a can be achieved. In t h i s work we examined c a t a l y s t s prepared i n two ways: according t o Ref. [7] (designated C a t a l y s t I) and according t o Ref. [ 8 ] (designated C a t a l y s t II). In t h i s a r t i c l e a study i s presented on the c a t a l y t i c gas-phase hydrogenation of benzene over copper c a t a l y s t s prepared according t o the p a t e n t s quoted above. A t t e n t i o n i s given a l s o t o t h e hydrogenation r a t e s of t h e I n t e r m e d i a t e s 1 ,M-cyclohexadiene and cyclohexene. The r e a c t i o n mechanism i s d i s c u s s e d , and modified Tanaka-Tamaru p l o t s [9] a r e c o n s t r u c t e d in which the a c t i v i t y of copper i s compared with the a c t i v i t y of o t h e r t r a n s i t i o n metals.

3.2 EXPERIMENTAL 3.2.1 M a t e r i a l s Benzene, cyclohexene and cyclohexane, a l l "fr d i e S p e c t r o s c o p i e " , were supplied by Merck, FRG. 1,4-Cyclohexadiene (purity 97%) was obtained from Aldrich Chemie, Belgium. After drying by adding an excess of "Drina", a 9:1 Pb/Na a l l o y from Merck, t h e l i q u i d s were f u r t h e r p u r i f i e d by d i s t i l l a t i o n in an u l t r a - p u r e Pyrex g l a s s a p p a r a t u s under oxygen-free n i t r o g e n . Desulphurization was c a r r i e d out by s l u r r y l n g for 30 min. with 4 g.dm -3 of

reduced ruthenium powder ( D r i j f h o u t , The N e t h e r l a n d s ) , with 2 -1 S(BET) = 6 m .g , under d r y , oxygen-free n i t r o g e n . According t o Don and Scholten [ 1 0 ] t h i s p u r i f i c a t i o n method leads t o a f i n a l thiophene c o n c e n t r a t i o n of l e s s than 0.1 ppm and an S0 2 content of l e s s than 0.2 ppm. Hydrogen and helium (99.9$) from Hoek Loos, The Netherlands, were p u r i f i e d from oxygen and water as d e s c r i b e d in Chapter 2 [ 1 1 ] . 2 -1 Shell s i l i c a s p h e r e s , type CLA 33570C, S(BET) = 265 m .g and average pore diameter 16 nm, were used a s the support m a t e r i a l . The diameter of the

31 spheres i s 3 mm. Copper n i t r a t e and ammonium bicarbonate (both r e a g e n t grade) were obtained from J . T . Baker, The Netherlands, and urea from Merck, FRG. 3.2.2 C a t a l y s t c h a r a c t e r i z a t i o n Pore volume d i s t r i b u t i o n s were determined from n i t r o g e n ad- and desorption isotherms a t 78 K, recorded by an adsorption a p p a r a t u s from Carlo Erba, I t a l y , type Sorptomatic. In the c a l c u l a t i o n s the c o r r e c t e d Kelvin equation according t o Broekhoff and de Boer [ 1 2 ] was a p p l i e d . Free-copper surface a r e a s were measured a f t e r r e d u c t i o n of the samples a t
3 -1

670 K for 3 hrs in hydrogen (60 cm (STP).min ) , followed by evacuation down -t to 10 Pa. Then, after cooling down to 363 K, successive doses of N-O were admitted, which decompose according to: 2 Cu + N0(gas) (Cu )_0 + N-(gas)
3 d
a d d

(1),

where Cu

i s a copper s u r f a c e s i t e .

By freezing o u t , a t 78 K, the N_0, t h a t remains a f t e r e q u i l i b r i u m has been reached, the amount of evolved n i t r o g e n corresponding t o t h e Cu ? 0monolayer i s found, from which t h e free-copper s u r f a c e a r e a i s c a l c u l a t e d [13]. BET surface areas were c a l c u l a t e d from n i t r o g e n a d s o r p t i o n isotherms a t 78 K, measured in a "micro-BET a p p a r a t u s " provided with a Baratron pressure gauge (MKS Instruments I n c . , USA) equipped with s i n g l e s i d e d s e n s o r s . After drying, the pore volumes of the c a t a l y s t s were determined by adding d i s t i l l e d water from a b u r e t t e u n t i l the caking point was r e a c h e d . Electron microscopy and XPS/AES surface a n a l y s i s were performed as described e a r l i e r [ 1 1 ] . The metal content of the c a t a l y s t was measured by means of atomic absorption spectroscopy, with a Perkin Elmer, type ^60, s p e c t r o m e t e r . For t h i s purpose t h e samples were decomposed f i r s t with a borax carbonate mixture.

3 . 2 . 3 Hydrogenatlon equipment The hydrogenation activities of the copper catalysts were determined in

35 continuous-flow equipment with a fixed-bed r e a c t o r , which i s described in Chapter 2 [ 1 1 ] . The r e a c t i o n p r e s s u r e could be v a r i e d from 100 t o 500 kPa and t h e r e a c t i o n temperature from 283 t o 800 K. Analysis of the r e a c t i o n p r o d u c t s was performed in a gas chromatograph equipped with a flame i o n i z a t i o n d e t e c t o r and a Hewlett Packard e l e c t r o m e t e r , type 5701 A. The column we used ( i n n e r diameter 3 m m and length 1 m) was f i l l e d with 30$ 1 , 2 , 3 - t r i s ( 2 - c y a n o e t h o x y ) p r o p a n e on Chromosorb W-HP, 80-100 mesh. Peak a r e a s were i n t e g r a t e d with a microprocessor LCI 11/03, from D i g i t a l Equipment C o . , USA. 3.2.1 Catalyst Catalyst I D e p o s i t i o n - p r e c i p i t a t i o n by means of t h e homogeneous decomposition of urea (Geus method, [ 7 ] ) was. performed in a double-walled g l a s s f l a s k with vigorous s t i r r i n g and with oxygen-free n i t r o g e n bubbling through the s o l u t i o n . In t h e flask 5.0 g of s i l i c a spheres and 8.0 g of urea were added 3 t o 900 cm of a 0.03 M c u p r i c n i t r a t e s o l u t i o n ; t h i s mixture was a c i d i f i e d t o pH=2 with 1.0 M HC1. Then t h e mixture was heated to 363 K by c i r c u l a t i n g heated o i l through t h e h e a t i n g j a c k e t . When f i n a l l y pH=6 was reached, t h e c a t a l y s t was f i l t e r e d off, a r a t e of 0.5 K.min washed thoroughly with d i s t i l l e d water and dried in a i r a t 100 K for 17 h r s . Next, the c a t a l y s t was heated a t 673 K in a i r at and c a l c i n e d under flowing a i r a t t h i s temperature for
3
_i _i

preparation

3 h r s . Then i t was cooled down t o room temperature and r e h e a t e d t o 673 K in a flow of hydrogen (60 cm (STP).min ) a t a r a t e of 0.5 K.min . The

c a t a l y s t was f u r t h e r reduced a t t h i s temperature for 3 h r s , then cooled down t o room temperature under hydrogen and f i n a l l y t h e hydrogen was slowly r e p l a c e d by a i r in o r d e r t o p a s s i v a t e t h e s u r f a c e of the copper p a r t i c l e s . Catalyst II The p r e p a r a t i o n of a copper c a t a l y s t according t o t h e afore-mentioned ICI p a t e n t [8] was. performed as f o l l o w s . An amount of 8.2 g of c u p r i c n i t r a t e 3 t r i h y d r a t e was d i s s o l v e d in 75 cm of d i s t i l l e d water and 5.5 g of s i l i c a spheres were added and mixed t h o r o u g h l y with the s o l u t i o n . The s l u r r y was 3 t r a n s f e r r e d t o a g l a s s f l a s k and 125 cm of a 1.2 M ammonium b i c a r b o n a t e s o l u t i o n was added dropwise over a period of one hour with vigorous s t i r r i n g , a t a temperature of 318 K. Next, the mixture was s t i r r e d and boiled for another hour. F i n a l l y the c a t a l y s t was f i l t e r e d off, washed

36
thoroughly with distilled water, and calcined and reduced as indicated for the catalyst prepared according to the Geus method.

3.3 RESULTS 3.3.1 Catalyst characterization The support

From an analysis of the ad- and desorption branches of the hysteresis loop of the nitrogen adsorption isotherm at 78 K, the pore volume distribution of the s i l i c a spheres was determined. As in the analysis of these branches the corrected Kelvin equation was applied, both branches yield the same pore volume distribution curve [14]. A very narrow distribution was arrived at around a pore diameter of 21 nm. The difference between t h i s diameter and the value given by the supplier (16 nm) is 24%. Therefore i t i s likely that the supplier's value was calculated according to the classical Kelvin equation. Indeed, according to Broekhoff s tables [ 1 4 ] , at a true pore diameter value of 21 nm the classical Kelvin equation should 2 -1 give a diameter which i s 21$ too low. The BET surface area (267 m .g ) i s 2 1 in good accordance with the s u p p l i e r ' s value (265 m .g ) . Catalyst II
After deposition of 14 wt$ copper on the support, following the ICI method (catalyst II), small changes in the texture could be detected: 2 S B E _ increased to 310 m per gram of support, the pore volume decreased from 1.47 to 1.33 cm per gram of support and the average pore diameter remained 21 nm. It follows that, applying this method, the support is mildly affected. Nevertheless a strong fixation of the copper particles is arrived at, as activity measurements up to 800 K did not point to any deactlvation due to copper sintering. The copper content of 14 wt$ in catalyst II was determined by atomic absorption spectrometry. After cutting the catalyst spheres in two parts a homogeneous copper distribution over the support is macroscopically observed (adoculos).
t

After reduction, adsorptive decomposition of N?0 a t 363 K resulted in a 2 free-copper surface area of 17.3 m per gram of c a t a l y s t . This corresponds 2 to 124 m copper per gram of copper, from which a volume surface mean

37
diameter, d , of 5.5 nm is calculated. Following the method explained in

Ref. [11] for the case of ruthenium, dv_ was calculated from TEM micrographs of a reduced catalyst encapsulated in a polymerized mixture of 70% methylmethacrylate and 30% butylmethacrylate; d M appeared to be (**1) nm, a value smaller than found with the N 2 0 method. This points to part of the copper surface being fixed to the support. Surface analysis of catalyst II by AES gave a Cu peak at 311.7 eV, and

pointed to the absence of impurities in the surface within the detection sensitivity of the method (0.1 a t % ) . In the XPS region only a very small peak of carbon at 965 eV was detected. Catalyst I Contrary to what was experienced in the preparation of catalyst II, the Geus method used for catalyst I led to an appreciable change of the texture 2-1 2-1 of the original support; S__ increased from 265 m .g to 371 m .g , the 3-1 3-1 pore volume decreased from 1.47 cm .g diameter from 21 nm to 12 nm. Atomic absorption spectrometry showed the copper content of the outer shell of the catalyst spheres (thickness 0.3 mm) to be about 20 wt$, whereas the core of the spheres had a copper content of 2 wt$. Hence, the catalyst has a mantle character. 2 The free-copper surface area found by the N_0 method was 1.6 m Cu per 2 gram of catalyst, corresponding to 66 m Cu per gram of copper. From this a d v value of 11.5 nm is calculated. After reduction AES analysis gave a Cu peak at 312.9 eV, and the only impurity detected was carbon (C(1s) peak at 965 eV). Catalyst I exhibited a poor mechanical strength; the shell crumbled off during reduction and during the hydrogenatlon experiments. Obviously this is due to the highly local character of the formation of copper hydroxy silicate, i.e. mainly in the shell of the particles. For this reason further experiments with catalyst I were abandoned. Here we only mention that the catalytic activity of catalyst I in the hydrogenation of benzene, at 300 K and 395 kPa (Hp/CgHg ratio is 11) and calculated per square meter freecopper surface area, was equal to that found with catalyst II under the same experimental conditions. to 1.10 cm .g and the mean pore

38
3.3.2 Kinetics of the hydrogenation of benzene The results of an activity and stability test in the benzene hydrogenation over catalyst II are plotted in Fig. 1. The experimental conditions are presented in the legend to the figure.

3.2
TON

i
WOK

2.4

(molecules C5H5 x10 3 .site" 1 .s" 1 ) 1.6 0.8 <

303 K
10-

6 12 18 24 reaction time (hrs)

30

36

42

FIGURE 1 The r a t e of benzene hydrogenation over c a t a l y s t I I (14 wt$ Cu-ons i l i c a ) as a function of r e a c t i o n t i m e , a t 303 K and a t 400 K. Total pressure 395 kPa, hydrogen pressure 393 kPa, benzene p r e s s u r e 3 2 2 kPa, space v e l o c i t y 505 cm (STP) per m free-copper surface a r e a per hour. Benzene conversion: 7% a t 303 K and 27% a t 400 K. . I t i3 seen from F i g . 1 t h a t the c a t a l y t i c a c t i v i t y i s s t a b l e for a t l e a s t 42 h o u r s , both a t 303 K and 400 K. The only product d e t e c t e d was cyclohexan. From the good s t a b i l i t y we conclude t h a t d e a c t i v a t i o n due t o the formation of by-products on t h e s u r f a c e , l i k e the a l k y l a t i o n products of benzene and cyclohexene, as observed i n the case of ruthenium [ 1 1 ] , does not occur with copper. The absence of benzene a l k y l a t i o n might be due t o t h e low a c t i v i t y of copper i n t h i s r e s p e c t , and/or t o t h e f a c t t h a t benzene and cyclohexene coverages during t h e r e a c t i o n . a r e a p p r e c i a b l y lower than in t h e case of ruthenium. The o r d e r s in hydrogen and benzene were s t u d i e d in t h e temperature range from 306 t o 400 K. The r e s u l t s of a l l measurements a r e given in F i g s . 2 and 3, t o g e t h e r with the experimental c o n d i t i o n s .

37
diameter, d v , of 5.5 nm is calculated. Following the method explained in Ref. [11] for the case of ruthenium, d was calculated from TEM micrographs of a reduced catalyst encapsulated in a polymerized mixture of 70$ methylmethacrylate and 30$ butylmethacrylate; d. appeared to be (H1) nm, a value smaller than found with the N ? 0 method. This points to part of the copper surface being fixed to the support. Surface analysis of catalyst II by AES gave a Cu peak at 31^.7 eV, and pointed to the absence of impurities in the surface within the detection sensitivity of the method (0.1 at$). In the XPS region only a very small peak of carbon at 965 eV was detected. Catalyst I Contrary to what was experienced in the preparation of catalyst II, the Geus method used for catalyst I led to an appreciable change of the texture 2-1 2-1 of the original support; S D __ increased from 265 m .g to 371 m .g , the 3-1 3-1 pore volume decreased from 1.47 cm .g diameter from 21 nm to 12 nm. Atomic absorption spectrometry showed the copper content of the outer shell of the catalyst spheres (thickness 0.3 mm) to be about 20 wt$, whereas the core of the spheres had a copper content of 2 wt$. Hence, the catalyst has a mantle character. 2 The free-copper surface area found by the N_0 method was 't.6 m Cu per p ^ gram of catalyst, corresponding to 66 m Cu per gram of copper. From this a d v value of 11.5 nm is calculated. After reduction AES analysis gave a Cu peak at 312.9 eV, and the only impurity detected was carbon (C(1s) peak at 965 eV). Catalyst I exhibited a poor mechanical strength; the shell crumbled off during reduction and during the hydrogenation experiments. Obviously this is due to the highly local character of the formation of copper hydroxy silicate, i.e. mainly in the shell of the particles. For this reason further experiments with catalyst I were abandoned. Here we only mention that the catalytic activity of catalyst I in the hydrogenation of benzene, at 300 K and 395 kPa (Hp/CgH, ratio is 11) and calculated per square meter freecopper surface area, was equal to that found with catalyst II under the same experimental conditions. to 1.10 cm .g and the mean pore

38
3.3.2 Kinetics of the hydrogenation of benzene The results of an activity and stability test in the benzene hydrogenation over catalyst II are plotted in Fig. 1. The experimental conditions are presented in the legend to the figure.

I 400 K

3.2 TON (molecules CgHg x10 3 .site~ 1 .s~ 1 ) 16


303 K 0.8
u

oI I

0 0

12

18

Ik

30

36

UL

reaction time (hrs) FIGURE 1 The r a t e of benzene hydrogenation over c a t a l y s t I I (1*1 wt$ Cu-ons i l i c a ) as a function of r e a c t i o n t i m e , a t 303 K and a t 400 K. Total pressure 395 kPa, hydrogen p r e s s u r e 393 kPa, benzene p r e s s u r e 3 2 2 kPa, space v e l o c i t y 505 cm (STP) per m free-copper surface a r e a per hour. Benzene conversion: 1% a t 303 K and 21% a t 400 K. I t i s seen from F i g . 1 t h a t t h e c a t a l y t i c a c t i v i t y i s s t a b l e for a t l e a s t 42 hours, both a t 303 K and 400 K. The only product d e t e c t e d was cyclohexane. From the good s t a b i l i t y we conclude t h a t d e a c t i v a t i o n due t o the formation of by-products on t h e s u r f a c e , l i k e t h e a l k y l a t i o n products of benzene and cyolohexene, as observed in the c a s e of ruthenium [ 1 1 ] , does not occur with copper. The absence of benzene a l k y l a t i o n might be due t o the low a c t i v i t y of copper i n t h i s r e s p e c t , and/or t o t h e f a c t t h a t benzene and cyolohexene coverages during the r e a c t i o n a r e a p p r e c i a b l y lower than in t h e case of ruthenium. The o r d e r s in hydrogen and benzene were s t u d i e d i n t h e temperature range from 306 t o 400 K. The r e s u l t s of a l l measurements a r e given in Figs. 2 and 3, t o g e t h e r with the experimental c o n d i t i o n s .

39

In TON

(molecules C5H5 site'V) -8.2 -8.6 -9.0 4.4 4.6 4.8 5.0 In PH2 (kPa) 5.2 5.4 5.6 5.8 6.0

FIGURE 2 The r a t e of benzene hydrogenation as a function of hydrogen pressure over catalyst I I , on a double logarithmic scale.Total pressure 395 kPa, hydrogen pressure.99 - 390 kPa, benzene pressure
3
2

5 kPa, space velocity 31*1* cm (STP) per m free-copper surface area per hour. Total pressure was reached in each case by adding helium gas t o the feed. The numbers between brackets indicate the reaction orders in hydrogen In the various pressure and temperature regions investigated. Fig. 2 demonstrates the order in hydrogen to be strongly temperature and pressure dependent. For Instance, at tOO K and at low pressure the order in hydrogen is i n i t i a l l y 2.5, but at higher pressures i t i s 0.7 only. At 315 K and at 306 K an analogous tendency is observed. Results of the experiments on the determination of the order in benzene are plotted in Fig. 3. Note that the variation in benzene pressure was much smaller than the variation in hydrogen pressure (Fig.2). Moreover, r e s u l t s in Fig. 3 are representative of experiments at a relatively high hydrogen pressure (330 kPa) with respect t o the benzene pressure.

1)0

-6.2

In TON (molecules CgH^. -7.4 site"1.s"1) -

FIGURE 3 The rate of benzene hydrogenation as a function of benzene pressure over catalyst II, on a double logarithmic scale. Total pressure 395 kPa, hydrogen pressure 330 kPa, benzene pressure 1.5 - 7.5 kPa, 3 2 space velocity 344 cm (STP) per m free-copper surface area per hour. In each case the total pressure was reached by adding helium gas to the feed. The numbers in brackets indicate the reaction orders in benzene in the various pressure and temperature regions. In determining the apparent activation energy a large number of experiments were performed at a large number of different temperatures, the temperatures used in Figs. 2 and 3 included. Results are plotted in Fig. 4. In cases like this it is necessary to plot the logarithm of the reaction rate constants as a function of the reciprocal temperature. These rate constants can be calculated from the data in the Figs. 2 and 3 by dividing the reaction rates by p H 2 times PC5H5- In doing so we calculated the orders B in hydrogen and o in benzene at various temperatures by interpolation between the orders found at 306, 345 and 400 K (Figs. 2 and 3). Fig. 4 shows two striking facts. First, the value of the apparent activation energy changes drastically in the temperature range from 330 to

11

Temperature (K) 435 400 370 345 9.0 10.0 11.0 In k (molecules _ 12 0 C6H6.site"1.s"1, divided by
_

323

303

13.0

IpC6H6lax [ P H 2 1 P ) 0 - 14.0 - 15.0 2.3 2.5 2.7 1000/T (K"1) 2.9 3.1 3.3 3.5

FIGURE 1 Arrhenius p l o t for t h e hydrogenation of benzene over 14 wt$ Cu-ons i l i c a . Total p r e s s u r e 395 kPa, hydrogen pressure 389 kPa, benzene 3 3 - 2 - 1 p r e s s u r e 6 kPa, space v e l o c i t y 1.6x10 cm (STP).m Cu.h . a i s the v a r i a b l e o r d e r i n benzene and 6 i s the v a r i a b l e order in hydrogen. The apparent a c t i v a t i o n e n e r g i e s a r e indicated between b r a c k e t s , in kJ.mol 370 K, from +58.1 kJ.mol" t o - 2 1 . 3 kJ.mol . Such behaviour has been

r e p o r t e d e a r l i e r for n i c k e l [ 1 5 ] , c o b a l t [16] and many o t h e r metals [17] and was found for ruthenium as well (see Chapter 2 ) . Secondly,the a c t i v a t i o n energy in t h e temperature range from 300 K t o 330 K (58.1 kJ.mol
[11]).

) is

r e l a t i v e l y high as compared with our r e s u l t with ruthenium ( 3 . 8 kJ.mol .

1)2

3 . 3 . 3 Temperature dependence of the hydrogenation r a t e s of 1 ,'t-cyclohexadlene and of cyclohexene From i n t r o d u c t o r y experiments over c a t a l y s t I I a t 300 K and 130 kPa and with a hydrogen t o s u b s t r a t e r a t i o of i7 the hydrogenation r a t e of cyclohexene was found t o be two hundred times as high a s the hydrogenation r a t e of benzene. Under the same c o n d i t i o n s the rate. Further i n v e s t i g a t i o n s on t h e behaviour of 1 ,'t-cyclohexadiene under hydrogenating conditions (see F i g . 5) showed t h a t both benzene and cyclohexene a r e produced, in n e a r l y equal amounts, and t h a t only small 1,4-cyclohexadiene hydrogenation r a t e i s four times as high as the cyclohexene hydrogenation

Temperature (K) 400 370 345 323 0 -2 -4 In (molecules CgHpi formed per site -6 per second) -8 " 2.5 2.7 2.9 1000/ T (K~1) 3.1

303

3.3

FIGURE 5 A p l o t of the r a t e s of product formation as a f u n c t i o n of 1000/T in the hydrogenation of 1,4-cyclohexadiene over 11 wt$ C u - o n - s i l i c a ( c a t a l y s t I I ) . 0 : benzene, X: cyclohexene and A: cyclohexane. Total pressure 130 kPa, hydrogen pressure 62 kPa, 1.6x10 3 cm 3 (STP).m" 2 Cu.h" 1 . 1,4-cyclohexadiene p r e s s u r e 2 kPa, helium p r e s s u r e 66 kPa, space v e l o c i t y

amounts of cyclohexane are produced. In Fig. 5 the production rates as a function of the reciprocal temperature are given. Note that we here arrived a t the same striking r e s u l t as with ruthenium [11]: during hydrogenation of 1, 4-cyclohexadiene a simultaneous dehydrogenation occurs. Just as in the case of ruthenium t h i s should be due to the high free enthalpy level of 1,1-cyclohexadiene with respect to the levels of both benzene and cyclohexene. Of course a kinetic analysis of the r e s u l t s , plotted in Fig. 5, is hampered by the fact t h a t , s t a r t i n g from 1,4-cyclohexadiene, three different products are formed, presumably via three different transition s t a t e s . I t is l i k e l y that the small amounts of cyclohexane are not a direct product from 1,4-cyclohexadiene hydrogenation, but are formed from cyclohexene.

Temperature (K) 455 417 385 357 333 313 294

In TON (molecules C0H-)o< site"1.s"1)

2.2 2.4 2.6 1 0 0 0 / T IK" 1 )

2.8

3.0

3.2

3.4

FIGURE 6 Arrhenius plot of the r a t e of hydrogenation of cyclohexene over catalyst I I . Total pressure 130 kPa, hydrogen pressure 62 kPa, cyclohexene pressure 6 kPa, helium pressure 62 kPa, space velocity 2.3 cm3(STP).m"2Cu.h"1.

Uk

Experiments on the hydrogenation of cyclohexene over catalyst II are presented in Fig. 6. Comparing the results with those for benzene hydrogenation near the maximum of the rates plotted in Fig. 4, it is immediately seen that the rates are faster by a factor of about two hundred. (According to the proposed mechanism, at temperatures higher than the temperature belonging to the maximum in the Arrhenius plot the hydrogenation of cyclohexene is the rate-determining step, see also section discussion.) Note, however, that due to the difference in experimental conditions with respect to benzene hydrogenation the coverage f copper with cyclohexene will be much higher under the conditions of Fig. 6. The apparent activation energy'amounts to 55 kJ.mol . In the temperature range from 291 to 357 K the apparent activation energy is nearly zero. An explanation for this requires a more complete kinetic analysis.

3.1 DISCUSSION 3.^.1 Kinetics of the hydrogenation of benzene, 1,1-cyclohexadiene and cyclohexene Copper is known to be a catalyst with a very low hydrogenation activity as compared with transition metals like, for instance, nickel and ruthenium. Notwithstanding this fact the preparation of a special catalyst, in which small copper crystallites with a mean diameter of 5.5 nm are strongly fixed to a sinter-resistant pure silica support, enabled us to study the kinetics of benzene hydrogenation at temperatures as low as 300 K. The excellent catalytic performance of catalyst II is caused by its large free-copper surface area and by the high percentage of surface copper planes with high Miller indices, the mean diameter of the copper crystallites being 5.5 nm. Besides the high mechanical and sintering stability of catalyst II the catalytic stability was excellent as well. This is due to the absence of poisoning side reactions like the alkylation of benzene by cyclohexene and the formation of carbonaceous deposits as observed in the case of ruthenium [11]. From a kinetic point of view, copper qualitatively behaves the same as ruthenium. On increasing the partial benzene pressure the order in benzene decreases from ca. 0.6 to 0.1, which points to a Langmuir-llke influence of

U5

the benzene coverage on the r a t e of reaction. Furthermore, as observed with ruthenium [ 1 1 ] , the order in hydrogen pressure increases from 1.5 at 306 K to the very high value of 2.5 a t 100 K, both at low p a r t i a l hydrogen pressure. Another striking analogy with the behaviour of ruthenium is the abrupt change of the apparent activation energy from positive to negative at a c r i t i c a l temperature (at 350 K in the case of copper). Also, just as we found with ruthenium, the r a t e s of hydrogenation of 1,4-cyclohexadiene and of cyclohexene are much faster than the r a t e of benzene hydrogenation, and starting from 1,4-cyclohexadiene both benzene and cyclohexene were formed. All these facts make i t plausible that the mechanism over copper i s essentially the same as the mechanism formulated for the case of ruthenium [11], viz. a stepwise addition of chemisorbed hydrogen atoms to chemisorbed benzene. W e shall now discuss the reaction mechanism over copper in more d e t a i l . The adsorption of benzene on the surface of transition metals i s believed to occur in the form of a threefold ir-bonded complex, with ir-electron donation to the empty d-orbitals of the surface metal atoms and back-donation of d-electrons to the anti-bonding o r b i t a l s of benzene [18]. Hence, the strength of chemisorption of benzene on transition metals will depend on the degree of d-orbital f i l l i n g of the metal and on the s p a t i a l extension of the d-orbitals. The lower the degree of d-orbital f i l l i n g , the more benzene will lose i t s aromatic character as a result of chemisorption [19,20]. This in turn causes a difference in r e a c t i v i t y of benzene with the adsorbed hydrogen atoms when applying different t r a n s i t i o n metals as hydrogenation c a t a l y s t s . In the case of copper we are dealing with completely f i l l e d d - o r b i t a l s . Though the situation with respect to the availability of bonding o r b i t a l s at the surface i s largely unknown, we speculate that with copper the formation of ir-complex bonds with benzene i s very limited. The weak substrate-metal interaction i s shown by the fact that only at 306 K and r e l a t i v e l y high benzene p a r t i a l pressures full coverage of benzene i s reached, which finds expression in the benzene reaction orders. However, according to the proposed reaction mechanism [11], the adsorption enthalpy of benzene has a higher absolute value than the adsorption enthalpy of cyclohexene. Hence, the benzene adsorption i s not determined by van der Waals interaction only. From the weak Interaction i t follows that after chemisorption benzene retains a large portion of i t s resonance energy and hence i t s reactivity

16
with chemisorbed hydrogen atoms is much lower than, for instance, on ruthenium as a catalyst. Of course, a second factor determining the lower hydrogenation activity of copper is the very low benzene coverage attending the low enthalpy of adsorption on copper. Another important difference between copper and many of the other transition metals lies in the mode of hydrogen chemisorption, as explained in the introduction. First, the extent of dissociative hydrogen chemisorption is limited to the high Miller index planes. Provided surface migration of hydrogen to the low index planes is absent, this means that the hydrogen coverage is very low and only about 0.15 to 0.20 [-21]. Secondly, the enthalpy of dissociative hydrogen chemisorption is low as compared with other transition-metals. For the high index (311) plane Pritchard mentions a value of -39.8 kj.mol hydrogen is 136 kj.mol [6], As the dissociation enthalpy of gaseous , it follows that 'the enthalpy of chemical bonding . For . Hence, the bonding

of two hydrogen atoms to the copper surface amounts to -475.8 kj.mol hydrogen on nickel this value is about -537 kj.mol

strength of hydrogen atoms on the high index planes of copper is about 14% lower than on nickel. Comparing copper with other transition metals, like nickel, the result is nearly the same [21]. One might expect that due to this the hydrogenation activity of adsorbed hydrogen atoms on copper is somewhat higher than on other transition metals. The relatively low activation energy for hydrogen chemisorption on copper (21 kj.mol a reaction rate retarding factor at very low temperatures only. In Chapter 2, dealing with benzene hydrogenation over ruthenium, we discussed the role of weakly chemisorbed hydrogen. There it was stated that this weakly bound form should have the highest hydrogenation activity [11]. Such a special form of chemisorbed hydrogen has never been detected on copper. -This means that the hydrogenation of benzene over copper runs via normal strongly bound chemisorbed hydrogen atoms which is a retarding factor as compared with the activity of the other transition metals. All in all, we think that the discussion of the mechanism and of the details of the kinetics should go along the same lines as presented for the case of ruthenium [11]; the differences are of quantitative nature. At the lowest temperatures investigated the first steps, the successive addition of two adsorbed hydrogen atoms to the adsorbed benzene, will be rate determining. In the case of copper the attending activation energy is ) will be

17
58 kj.mol whereas in the case of ruthenium 4 kJ.mol was arrived at. It

follows that hydrogenatlon of the benzene nucleus, which still retains a large portion of its resonance energy, is kinetically much more difficult. As argued for the case of ruthenium [11] the sudden change of the apparent activation energy around 350 K, attended with a strong increase of the order in hydrogen pressure, may be explained from the very low coverage of cyclohexene at higher temperatures on account of which the last step, the hydrogenatlon of cyclohexene, becomes the slowest and hence rate-determining step. The high order in hydrogen is caused by the two preceding hydrogenatlon reactions, which are now nearly in equilibrium and both first order in hydrogen pressure. The only difference with respect to the results found over ruthenium is the decrease in hydrogen order at relatively high hydrogen pressures. This might be explained as follows. Possibly surface migration of hydrogen to the low Miller index planes occurs at high hydrogen pressures, which forces the benzene to adsorb as an overlayer over the adsorbed hydrogen atoms, just as proposed for the case of ruthenium [11]. Because of the low bonding ability of copper, adsorbed hydrogen may modify the properties of the surface copper atoms in such a way that the interaction between benzene and the metal diminishes, which leads to decreasing reactivity of the adsorbed molecule. An indication in this direction was found by Erkelens and Eggink-du Burck [22], who studied the adsorption of benzene on copper by means of infrared spectroscopy. In the absence of hydrogen the spectrum shows benzene, adsorbed with loss of aromatic character. However, when hydrogen is admitted, peaks representing aromatic C-H stretch vibrations appear. This phenomenon explains the observed decrease in hydrogen order at relatively high hydrogen partial pressures; the decrease in reactivity of adsorbed benzene leads to the first hydrogen addition step to be rate-determining again, which results in a decrease of hydrogen order. 3.^.2 Tanaka-Tamaru plots For many catalytic reactions an intercomparison of the activities of the catalysts can be made in the form of so-called Tanaka-Tamaru plots [9]. In such plots the catalytic activities of the metals are plotted as a function of the enthalpy of formation of the corresponding bulk oxides of the metals. In doing so, volcano-shaped curves are obtained. The shape of these curves

18

2 0 T0N

1 2 0

-RuWV Rh (45)/ Pd(46Th


^

[nr

m e t a l ] TON Ru

-2

Co(27)/ \ N J

(28)
[n

-u
-6

\
Fe(26)/
l i

r T 0 N metal' L T0N R u .

2 U 6
C/TC{43)

Cu(29\
I ^ l

i'

5 7 9 number of d-electrons fourth period

5 7 9 number of d - electrons fifth period

Figure 7

Figure. 7

,[ TONmefatl TON
Ru

5 7 9 number of d-elecfrons sixth period.

Figure 7 FIGURE 7 Tanaka-Tamaru plots for the hydrogenation of benzene over several silica-supported transition metals at 373 K. expresses in a modern way what was stated already by Sabatier and Senderens in 1901 [23], namely that the bonding of the reaction partners to the surface of a catalyst should neither be too weak nor too strong in order to arrive at a high reaction rate.

19
For the case of benzene hydrogenation we thought It to be more relevant, on the basis of the discussion given above for the adsorption of benzene, to choose the degree of d-orbital filling as the characteristic parameter, instead of the enthalpy of formation of the corresponding oxides. Results for the rate of hydrogenation of benzene over transition metals of, successively, the fourth, fifth and sixth period of the periodic system are presented in Fig. 7, in which the logarithm of the reaction rate, relative to the rate over ruthenium as a reference, is plotted as a function of the number of d-electrons. In the plots the atomic number of the element in question is indicated. The rate data are taken from Refs. [16], [17], [24] and [25] for the activity of silica-supported metals per unit freemetal surface area in experiments at 373 K and at atmospheric pressure. Data for ruthenium, copper and rhodium stem from our own experiments. Interestingly, the three plots do not overlap; the higher the period number, the higher the activity of the metals. This is likely to be due to the increasing spatial extension of the d-orbitals with increasing period number. Further we note that the maxima in the three curves are found at nearly the same number of d-electrons. The results underline the decisive role of the strength of adsorption of benzene for the catalytic rate of reaction; too low a bonding strength (Cu) suppresses the rate of reaction and the same is the case for too high a bonding strength (Fe), in accordance with the Sabatier-Senderens rule.

ACKNOWLEDGEMENTS We thank Mr. A.P. Pijpers and Mr. J. Cremers (Department of Physical Chemistry, Central Laboratories, DSM, Geleen, The Netherlands) for the XPS/AES measurements and for their help with the interpretation of the spectra. Thanks are also due to Mr A. Pijpers, from the same department, for the TEM micrographs. Mr. J. Teunisse and Mr. N. van Westen, from Delft University of Technology, carried out the texture measurements of the catalysts. The investigations were supported (partly) by The Netherlands Foundation for Chemical Research (SON) with financial aid from The Netherlands Organization for the Advancement of Pure Research (ZWO).

50

REFERENCES

1 R. Pearce and W.R. P a t t e r s o n , " C a t a l y s i s and Chemical P r o c e s s e s " , Leonard H i l l , Glasgow, 1981. 2 L.E. Johansson and S.T. Lundin, J . Am. Oil Chem. S o c , 56 (1979) 9 7 1 . 3 L. Babernlcs, P. Tetenyi and L. Kortesz, Z. Phys. Chem. Neue Folge, 89 (1974) 237. 4 J.H. Long, J.C.W. Frazer and E . J . O t t , J. Am. Chem. S o c , 56 (1934) 1101. 5 R.J. Mikovsky, M. Boudart and H.S. Taylor, J. Am. Chem. S o c , 76 (1954) 3811. 6 J . P r i t c h a r d , T. G a t t e r i c k and R.K. Gupta, Surf. S c i . , 53 (1975) 1. 7 J.W. Geus, Dutch Patent No. 143.139 (St ami car bon). 8 J. Dewing, J . F . Ruddlesden, A. Stewart and D.J. Thompson, European P a t e n t No. 0006313, May 1979. 9 K . I . Tanaka and K. Tamaru, J . C a t a l . , 2 (1967) 8. 10 J.A. Don and J . J . F . Scholten, Faraday Discuss. (Chem. S o c ) , 72 (198.2) 145. 11 M.C. Schoenmaker-Stolk, J.W. Verwijs, J.A. Don and J . J . F . accepted for p u b l i c a t i o n in Applied C a t a l y s i s . 12 J . C . P . Broekhoff and J.H. de Boer, J. C a t a l . , 9 (1967) 8. 13 J.W. Evas, M.S. Wainwrlght, A.J. Bridgewater and D.J. Young, Appl. C a t a l . , 7 (1983) 75. 14 J . C . P . Broekhoff, Ph. D. Thesis, Delft University of Technology, 1969. 15 R.Z.C. van Meerten and J.W.E. Coenen, J . C a t a l . , 37 (1975) 37. 16 W.F. Taylor and H.K. Staff i n , J . Phys. Chem., 71 (1967) 3314. 17 H. Kubicka, J . C a t a l . , 12 (1968) 223. 18 R.S. Mulliken, J . Am. Chem. S o c , 74 (1952) 8 1 1 . 19 D.M. Haaland, Surf. S c i . , 102 (1981) 405. 20 S. Lehwald, H. Ibach and J . E . Demuth, Surf. S c i . , 78 (1978) 577.. 21 J . J . F . Scholten, A.P. P i j p e r s and A.M.L. Hustings, C a t a l . R e v . - S c i . Eng., 27 (1985) 151. 22 J. Erkelens and S.H. Eggink-du Burck, J. C a t a l . , 15 (1969) 62. 23 P. S a b a t i e r and J . B . Senderens, Compt. Rend., 132 (1901) 210. 24 C. Bolivar, H. Charcosset, R. F r e t y , L. Tournayan, C. Betizeau, G. Leclercq and M. Maurel, J . C a t a l . , 45 (1976) 179. 25 K.J. Yoon and M.A. Vannice, J. C a t a l . , 82 (1983) 457. Scholten,

51

C H A P T E R

1)

GAS-PHASE HYDROGENATION OF BENZENE OVER SILICA SUPPORTED Ru-Cu CATALYSTS by M.C. Schoenmaker-Stolk, J.W. Verwijs and J . J . F . Department of Chemical Technology, Delft U n i v e r s i t y of Technology, J u l i a n a l a a n 136, 2628 BL D e l f t , The N e t h e r l a n d s . Scholten

*)

ABSTRACT

A study has been made of the gas-phase hydrogenation of benzene over silica-supported Ru-Cu catalysts in the temperature range from 300 to t00 K and at a total pressure of 130 kPa. Special attention has been given to the catalytic stability and the activity of the catalysts as compared with monometallic supported ruthenium and copper catalysts, described in previous articles. Via a reductive deposition technique copper was deposited on silicasupported ruthenium catalysts. Two bimetallic catalysts were prepared, one with about 10$ of the ruthenium surface covered by copper and one with about 70$ copper coverage. The texture of the catalysts was studied by means of mercury penetration, nitrogen physisorption, hydrogen chemisorption and transmission electron microscopy, whereas surface analysis was performed by XPS/AES. At 11$ copper coverage a shift in the copper electron binding energy is observed, pointing to a small electron transfer from ruthenium to copper, but at 68$ copper coverage this shift has disappeared.

Paper submitted for publication in Applied Catalysis.

52

Copper d e p o s i t i o n on ruthenium i n c r e a s e s the l i f e - t i m e of t h e c a t a l y s t s c o n s i d e r a b l y without s e r i o u s l y a f f e c t i n g the a c t i v i t y per ruthenium s u r f a c e atom. At low copper coverage the r e a c t i o n k i n e t i c s are very s i m i l a r t o t h e k i n e t i c s found w i t h ruthenium, but a t high copper coverage t h e small s i z e of t h e ruthenium ensembles i n f l u e n c e s t h e k i n e t i c s c o n s i d e r a b l y .

14.1 INTRODUCTION In Chapters 2 and 3 [ 1 , 2 ] we r e p o r t e d on our study of the gas-phase hydrogenation of benzene over s i l i c a - s u p p o r t e d ruthenium and copper c a t a l y s t s , g i v i n g s p e c i a l a t t e n t i o n t o t h e r e a c t i o n mechanism and the k i n e t i c s of the r e a c t i o n . Our experiments showed ruthenium t o be one of t h e most a c t i v e c a t a l y s t s in the hydrogenation of benzene, whereas copper e x h i b i t s very poor a c t i v i t y . N e v e r t h e l e s s , t h e use of copper as a c a t a l y s t has some advantages as t h i s metal shows p e r f e c t c a t a l y t i c s t a b i l i t y and no by-products are formed [ 2 ] . Ruthenium, though very a c t i v e , i s u n s t a b l e , and t h i s i s mainly due t o t h e formation of s t r o n g l y adsorbed b y - p r o d u c t s , cyclohexylcyclohexane and 1,4-dicyclohexylcyclohexane, benzene and the r e a c t i o n i n t e r m e d i a t e cyclohexene [ 3 ] . I t i s the aim of the p r e s e n t Chapter t o r e p o r t on an i n v e s t i g a t i o n of the c a t a l y t i c performance of b i m e t a l l i c c a t a l y s t s of ruthenium and copper on s i l i c a as a support in t h e hydrogenation of benzene. I t i s i n t e r e s t i n g t o know in how f a r , by combining both m e t a l s , a c a t a l y s t i s obtained which i s a c t i v e and c a t a l y t i c a l l y s t a b l e as w e l l , and which i s i n a c t i v e in the formation of b y - p r o d u c t s . The hydrogenation of benzene over b i m e t a l l i c c a t a l y s t s has been i n v e s t i g a t e d for many y e a r s . In most cases group VIII m e t a l s , l i k e n i c k e l , platinum and palladium, a r e combined with group IB m e t a l s l i k e copper and g o l d . Ponec [ 4 ] and Hoang-Van, Tournier and Teichner [ 5 ] , in studying platinum-gold c a t a l y s t s , and A l l i s o n and Bond [6] for t h e case of palladiumg o l d , observed a d e c r e a s i n g c a t a l y t i c a c t i v i t y with i n c r e a s i n g gold p e r c e n t a g e . Gold accumulates a t the s u r f a c e of these group VIII m e t a l s , but t h e a t t e n d i n g d e c r e a s e in c a t a l y t i c a c t i v i t y i s not simply p r o p o r t i o n a l t o t h e e x t e n t of the non-covered p a r t of the platinum and palladium s u r f a c e . An like which a r e formed from

53

increasing apparent activation energy i s observed with increasing gold coverage [ 4 ] , Furthermore, Hoang-Van c . s . , in studying platinum-gold, did not find a stabilizing effect of gold in the hydrogenation of benzene. In the l i t e r a t u r e much attention i s given to the bimetallic system nickel-copper. As found for platinum-gold and for palladium-gold, the catalytic activity in the hydrogenation of benzene decreases with an increase of the copper/nickel r a t i o , but t h i s is the case only at low temperatures. At high temperatures, around 600 K, the activity of the nickel-copper combination is higher than that of pure nickel [ 7 , 8 ] . Bond reports that at 425 and at 463 K the a c t i v i t y f i r s t increases with increasing copper content, then passes through a maximum at 25 per cent of copper, and subsequently f a l l s smoothly to about zero for pure copper [ 9 ] . Concerning the apparent activation energy, the behaviour of the nickelcopper system resembles that of platinum-gold and palladium-gold: when the copper/nickel r a t i o i s increased the apparent activation energy increases. As far as we know, the catalytic performance of the bimetallic catalyst ruthenium-copper in the hydrogenation of benzene has not yet been investigated. Much information on the behaviour of ruthenium-copper in other catalytic reactions i s available [10,11], however, and the studies by Sinfelt [12] on the hydrogenolysis of ethane and on the dehydrogenation of cyclohexane are well-known. The mutual solubility of ruthenium and copper i s very low: in the phase diagram an extremely wide miscibility gap i s observed [13]. However, at the surface of ruthenium the ruthenium-copper bond i s stronger than the coppercopper bond [11]. According to Christmann c . s . [14] copper is chernisorbed on ruthenium. At low copper coverages a homogeneous dispersion of copper is formed, but increasing copper coverage r e s u l t s in the formation of copper islands and only at a coverage of nearly one the formation of multilayers starts. A p a r t i a l coverage of ruthenium with copper may evoke the so-called ensemble size effect [ 3 , 1 5 ] . It i s to be expected that on small ruthenium ensembles the formation of by-products in the hydrogenation of benzene, like cyolohexyl- and 1,4-dicyclohexylcyclohexane, is s t e r i c a l l y hindered, so that catalytic behaviour will be s t a b l e . From the l i t e r a t u r e the impression i s gained that the influence of copper on the a c t i v i t y of surface ruthenium atoms and vice versa i s very small.

54

From XPS core l e v e l binding e n e r g i e s in t h e ruthenium-copper system no evidence was found of e l e c t r o n t r a n s f e r from copper t o ruthenium or v i c e versa [ 1 5 ] . However, upon d e p o s i t i o n of copper on a clean Ru(0001) s u r f a c e the work function i n c r e a s e s , which i s an i n d i c a t i o n of a s l i g h t t r a n s f e r from ruthenium t o copper [ 1 4 ] . We conclude t h a t be expected. With regard t o t h e p r e p a r a t i o n ' technique of b i m e t a l l i c c a t a l y s t s , most i n v e s t i g a t o r s apply dry impregnation of a mixture of s a l t s of t h e m e t a l s . As w i l l be explained in the s e c t i o n Experimental, in the work p r e s e n t e d h e r e an e s s e n t i a l l y d i f f e r e n t technique i s used. electron significant

e l e c t r o n i c e f f e c t s in the c a t a l y t i c behaviour of ruthenium-copper a r e not t o

4.2 EXPERIMENTAL 4.2.1 M a t e r i a l s Benzene, "fiir d i e S p e c t r o s c o p i e " , supplied by Merck, FRG, was f u r t h e r p u r i f i e d by adding an excess of Drina, a 9:1 Pb/Na a l l o y from Merck, followed by d i s t i l l a t i o n in an u l t r a - p u r e Pyrex g l a s s a p p a r a t u s under oxygen-free n i t r o g e n as a s h e l t e r g a s . The l a s t t r a c e s of s u l p h u r - c o n t a i n i n g -3 components were removed by s l u r r y i n g the benzene with 4 g.dm of reduced 2 -1 ruthenium powder (Drijfhout, The N e t h e r l a n d s ) , with S(BET) = 6 m .g , under dry, oxygen-free n i t r o g e n for 30 min. This leads t o a f i n a l c o n c e n t r a t i o n of s u l p h u r - c o n t a i n i n g components of l e s s than 0.3 ppm [ 1 7 ] . Hydrogen, 99.9$ p u r e , from Hoek Loos, The Netherlands, was p u r i f i e d from oxygen by l e a d i n g i t over a Pd/AIJD c a t a l y s t (BASF, FRG, t y p e R-020). Helium (99.9% p u r e , from Hoek Loos, The Netherlands) was made oxygen-free by l e a d i n g i t over a f i n e l y d i s p e r s e d c o p p e r - o n - s i l i c a c a t a l y s t , from BASF, FRG, type R-3-111. Both gases were dried over molecular s i e v e s type 3A. As support m a t e r i a l we used S h e l l s i l i c a s p h e r e s , type CLA 33569, mean p a r t i c l e diameter 3mm. According t o the manufacturer the average pore diameter i s 53 nm and S(BET) = 130 m .g~ . Ruthenium t r i c h l o r i d e (spec pure) was supplied by D r i j f h o u t , Netherlands. The Netherlands, and copper n i t r a t e was obtained from J . T . Baker, The

55

1.2.2 Catalyst preparation First two supported ruthenium catalysts, viz. 0.5 wtif Ru-on-silica and 3 wt$ Ru-on-silica, were prepared by means of the incipient wetness method (dry impregnation) [18]. After determination of the pore volume of the dried support by adding d i s t i l l e d water up to the caking point, a volume of ruthenium trichloride solution equal to t h i s pore volume was added. For the two catalysts ruthenium trichloride solutions of, respectively, 0.06 M and 0.34 M were used. These solutions were slowly added with continuous s t i r r i n g of the pre-dried s i l i c a . Next, the samples were dried in air at 400 K for 17 hrs and then the catalysts were heated to 673 K in a stream of hydrogen 3 -1 -1 (60 cm (STP).min ) at a heating rate of 0.5 K.min . The reduction was continued for 3 hrs at 673 K. Finally the catalysts were cooled down to room temperature in hydrogen. Starting from these ruthenium catalysts, ruthenium-copper catalysts were prepared in the following way. The reduced 0.5 wt$ Ru-on-silica catalyst was 3 -5 brought in a vessel f i l l e d with 100 cm of a 6x10 M copper n i t r a t e solution, under oxygen-free nitrogen as a shelter gas (catalyst A). Likewise 3 -3 the reduced 3 wt$ Ru-on-silica catalyst was added t o a 100 cm 2x10 M copper n i t r a t e solution (catalyst B). Both solutions were kept at 315 K and hydrogen was bubbled through with vigorous s t i r r i n g . Under these conditions 2+ hydrogen reduces the Cu ions to Cu, the ruthenium surface acting as a reduction catalyst and as the recipient of the copper atoms. Provided the free-ruthenium surface area i s known, pre-chosen copper-to-ruthenium ratios can be realized in t h i s way. As stated in the introduction, the copper atoms are chemisorbed on the ruthenium surface. The amount of copper taken up by the surface of the ruthenium particles was calculated from the spectrophotometrically measured decrease of the copper ion concentrations in the copper n i t r a t e solutions. It appeared that practically a l l copper from the solutions was deposited. Use was made of a Beekman spectrophotometer, model 35, monitoring the copper absorption line a t X = 745 nm. Fig. 1 represents the decrease of the copper ion concentration during the reductive copper deposition (catalyst B). The fact that the copper concentration decreases almost linearly with time points to chemisorption of copper being the r a t e determining s t e p , instead of diffusion of copper ions to the ruthenium surface.

56

Cu concentration in solution 1 3 (Mx10 )

0 0 20 " time (min)


FIGURE 1 The decrease of the Cu
2+

"40

* 60

concentration in the solution during the

preparation of catalyst B, measured spectrophotometrically. After copper deposition had been completed, the catalysts were thoroughly washed with distilled water, in order to remove possible traces of copper nitrate physically adsorbed on the support. The catalysts were then dried in air at MOO K for 17 hrs, After which reduction was carried out in a stream of hydrogen (60 cm (STP).min ) at 673 K for 3 hrs. After reduction the catalysts were cooled down to room temperature in hydrogen and, in order to passivate the samples, the hydrogen gas was slowly replaced by air. 4.2.3 Texture and surface composition The pore volume distribution of the silica was determined by means of mercury penetration in the range of pressures from 0.1 up to 200 MPa, applying a Porosimeter, type 2000, from Carlo Erba, Italy. Free-metal surface areas were determined from the extent of strong

57 hydrogen chemisorption as described previously [ 1 ] . BET s u r f a c e a r e a s were c a l c u l a t e d from nitrogen a d s o r p t i o n isotherms a t 78 K, t a k i n g for t h e c r o s s - s e c t i o n a l a r e a of a nitrogen molecule 0.162 nm . Surface a n a l y s e s were c a r r i e d out in a type LHS-10 XPS/AES apparatus from Leybold Heraeus, FRG. A MgKa e x c i t a t i o n source (energy 1253-6 eV) was applied a t the o p e r a t i n g c o n d i t i o n s of 1 3 kV and 20 mA. Samples were p r e t r e a t e d in vacuo or prereduced a t 670 K in a 90$ Ar + 10$ H? mixture in a p r e p a r a t i o n chamber, which was connected t o the XPS/AES chamber via a valveless U H V lock. TEM micrographs of the reduced and p a s s i v a t e d c a t a l y s t s were taken with a Philips E M 420T a p p a r a t u s . The c a t a l y s t s were mortared and embedded in a 70? methylmethacrylate + 30$ b u t y l m e t h a c r y l a t e m i x t u r e . After c u r i n g , 70 nm t h i c k s l i c e s were cut with an u l t r a microtome ( U l t r a c u t E, R e i c h e r t ) with a diamond c u t t e r . 4 . 2 . 4 Hydrogenatlon equipment The performance of the c a t a l y s t s in the gas-phase hydrogenation of benzene were t e s t e d in continuous-flow fixed-bed r e a c t o r equipment described i n Chapter 2 [ 1 ] . The t o t a l p r e s s u r e was kept constant a t 130 kPa and the r e a c t i o n was s t u d i e d in the temperature range from 290 t o 400 K. The composition of t h e product stream was analysed gas chromatographically, applying a flame i o n i z a t i o n d e t e c t o r and a Hewlett Packard e l e c t r o m e t e r , type 5704A. The column in t h e gas chromatograph had a l e n g t h of 4 m and an i n s i d e diameter of 3 mm; i t was f i l l e d with 30$ 1 , 2 , 3 - t r i s ( 2 - c y a n o ethoxy)propane on Chromosorb W-HP, 80-100 mesh. The peaks were i n t e g r a t e d with a microprocessor from D i g i t a l Equipment Co, USA, type LCI 1 1 / 0 3 .

4 . 3 RESULTS A N D DISCUSSION 4.3.1 Catalyst characterization

Data on t h e composition and t e x t u r e of the c a t a l y s t s a r e summarized in Table 1. The BET s u r f a c e a r e a of the support was not measurably influenced by the d e p o s i t i o n of 0.5 wt$ of ruthenium (see column 2 in Table 1; p r e c u r s o r of c a t a l y s t A), nor by t h e subsequent d e p o s i t i o n of copper (see c a t a l y s t A).

58

TABLE 1 C h a r a c t e r i z a t i o n of the s u p p o r t , the 'ruthenium precursor and t h e ruthenium-copper c a t a l y s t s . column 1


sample

catalysts

2
S(BET)

3
a)

1
d
b)

5
SC) H

6
Dd) M Cu/Ru
e)

7
Cu/Ru
f)

from g ^ from"' H ads TEM

s i l i c a support p r e c u r s o r of catalyst A catalyst A precursor of catalyst B catalyst B

115 115 115 n.m. n.m.

50 50 50 n.m. n.m.

n.a. 100 n.m. 80 n.m.

n.a. 0.28 0.28 0.224 0.224

n.a. 0 0.031 0 0.154

n.a. 0 0.11 0 0.618

n.a. 4.8

n.a. 2.6 2.6

6.0

-5

2.5

n.m. = not measured n.a. = not applicable

2 -1 a) BET surface a r e a per gram of c a t a l y s t i n m .g . b) mean pore diameter i n nm.


2 -1

c) free-ruthenium s u r f a c e area per gram of ruthenium i n m .g d) m e t a l l i c d i s p e r s i o n . e) copper/ruthenium r a t i o . f) copper/ruthenium r a t i o on the s u r f a c e . g) volume-surface mean diameter, c a l c u l a t e d from hydrogen chemisorptlon, in nm. h) volume-surface mean diameter, c a l c u l a t e d from TEM micrographs, i n nm. For the precursor of c a t a l y s t B and for c a t a l y s t B, with 3 wt$ ruthenium, the BET surface a r e a was not measured, but i t I s t o be expected t h a t t h e i n f l u e n c e of ruthenium and copper d e p o s i t i o n on S(BET) i s very s m a l l . Mercury p e n e t r a t i o n showed the support and c a t a l y s t s t o have a narrow pore volume d i s t r i b u t i o n with a maximum a t a pore diameter of 50 nm (column 3 ) , in accordance with t h e value mentioned by t h e s u p p l i e r .

59 From the free-ruthenium surface a r e a s (column ^) the m e t a l l i c d i s p e r s i o n , D.,, t h e number of s u r f a c e metal atoms divided by the t o t a l number of metal
M

atoms, was calculated. After deposition of copper on the precursor catalysts, no change in the metal particle size distribution was observed with the electron microscope; therefore in Table 1 the same metallic dispersions as found for the precursor catalysts are mentioned for catalysts A and B. Bearing in mind the immiscibility of ruthenium and copper in the bulk, we calculated the copper surface coverage on ruthenium from the total amount of copper atoms taken up (see column 7 in Table 1 ) . In calculating this 19 2 coverage, a number of ruthenium atoms of 1.63x10 per m was assumed. Catalyst B is distinct from catalyst A in that the ruthenium load is 6 times as high and the copper coverage 6.2 times as high. In columns 8 and 9 of the table the volume-surface mean diameters of the ruthenium crystallites, as calculated from the extent of the strong hydrogen chemisorption and from the total number of ruthenium atoms, are compared with the values found from electron microscopy. Just as reported for the copper and ruthenium catalysts described in Chapters 2 and 3 [1,2], dv_ found from TEM is much smaller than the cL value calculated from strong hydrogen chemisorption. This points to a large part of the metal crystallite surface being bound to the support, which part is inaccessible to hydrogen chemisorption. A TEM micrograph of catalyst A is given in Fig. 2. The cLg value of 2.6 nm was calculated from this photograph from a sample of 500 particles. It is seen that the metal particles are homogeneously distributed over the support. The TEM micrograph of catalyst B is presented in Fig. 3. From this a d value of 2.5 nm is arrived at from a sample of 350 particles, excluding the particles concentrated in clusters. This value is very near to the value found for catalyst A, which means that the higher metal loading (by a factor six) for this sample hardly influenced the metal dispersion; it only resulted in clustering of part of the crystallites.

60

FIGURE 2 TEM micrograph of catalyst A.

61

FIGURE 3 TEM micrograph.of catalyst B.

62
4.3.2 XPS/AES surface analysis XPS/AES spectra of the reduced catalysts A and B (see Fig. 4, catalyst B) show peaks of silicon, oxygen and ruthenium in normal positions, equal to those of reference samples. Furthermore, indications are found of the presence of extremely small amounts of sodium and carbon impurities.

CPSxIO4

260
k.energy eV

520

780

1040

1300

FIGURE 4 XPS/AES spectrum of the reduced catalyst B. The binding energies of electrons from the 2P and 2P levels of

copper are presented in Table 2. For catalyst A, with a copper coverage on ruthenium of only 0.11, electron binding energy shifts of -3.2 eV (2P. level) and -3.7 eV (2? level) are observed, whereas for catalyst B, with the high copper coverage on ruthenium of 0.68, an electron binding energy shift is absent. This phenomenon can be explained as follows. As stated in the Introduction, at low copper coverage a homogeneous distribution of chemisorbed copper atoms is present on the ruthenium surface. At a coverage of 0.11 these copper atoms are present as

63 TABLE 2 Cu(2P ) and Cu(2P ) electron binding energies (in eV), for reduced catalysts A and B. electron level Cu(2P 1/2 ) Cu(2P 3/2 ) catalyst A catalyst B pure copper (reference sample) 952.5 932.6

919.3 928.9

952.5 932.6

"singletons" and therefore copper-copper, interaction i s impossible. From the increase of the work function (see Introduction) we know that in this situation a slight electron transfer from ruthenium to copper occurs, and apparently t h i s i s the reason for the observed lowering of the electron binding energies. For catalyst B, with the high copper coverage of 0.68, copper islands are present and now a strong l a t e r a l copper-copper interaction e x i s t s . Though bonding to the ruthenium surface i s s t i l l present, t h i s l a t e r a l interaction largely compensates the energy s h i f t , and the energy levels are the same as found for pure copper. 1.3.3 S t a b i l i t y and a c t i v i t y of the catalysts in benzene hydrogenation In Fig. 5 the turn-over numbers for the. hydrogenation of benzene are plotted as a function of reaction time for catalysts A and B. The reaction conditions are given in the legend to the figure. For the sake of comparison, r e s u l t s for 0.5 wt$ Ru-on-silica and 11 wtjf Cu-on-silica, reported in Chapters 2 and 3 [ 1 , 2 ] , are plotted also in Fig. 5. The turn over numbers are calculated per number of ruthenium surface atoms. The following s t r i k i n g facts emerge: a) Copper chemisorbed on ruthenium, both at low coverage (0.11, catalyst A) and at high coverage (0.68, catalyst B), has a s t a b i l i z i n g effect on the catalytic a c t i v i t y in the hydrogenation of benzene. b) In the presence of copper on ruthenium, copper being a metal with a very low hydrogenation a c t i v i t y , the a c t i v i t i e s of catalysts A and B per ruthenium surface s i t e are i n i t i a l l y of the same order as that of pure ruthenium-on-silica. Comparing the i n i t i a l a c t i v i t y of catalyst A with the i n i t i a l a c t i v i t y value of 0.5 wt Ru-on-silica, catalyst A is 2.6 times as active as monometallic ruthenium c a t a l y s t . On the other hand,

64
the activity of catalyst B is nearly equal to the initial activity of the ruthenium catalyst. In our view the strong gain in catalytic stability for both catalysts A and B has to be ascribed to the ensemble size effect. For catalyst A, with its 11% copper coverage and its homogeneous copper distribution, the ensemble size will be of the order of 15 to 20 ruthenium atoms. This hampers the formation of large poisoning by-products like cyclohexylcyclohexane and 1,4-dicyclohexylcyclohexane, for which ensembles of circa 16 and 24 ruthenium atoms are necessary. We finally remark that experiments carried

I I catalyst A
B

I -O-O-o-r-

-2,
atalyst >c-~0-_o_o_0_o__f4_J

-4

^Sx
-6

0.5wt%Ru/Si02

In TON [molecules CgHg site~1.s"1) -8


0 14wt%Cu/Si02 I l 12 24 reaction time (hrs) i I

48 60

36

FIGURE 5 Turn-over numbers (molecules C..H, per ruthenium s i t e per second) as a function of r e a c t i o n time for the hydrogenatlon of benzene. Temperature 300 K, t o t a l p r e s s u r e 105 kPa, hydrogen p r e s s u r e 37 kPa, benzene p r e s s u r e 2 kPa, helium p r e s s u r e 66 kPa, flow r a t e 35 om 3 (STP).min" 1 .

65 out a t J400 K l e d t o the same conclusions as the experiments a t 300 K, p l o t t e d in F i g . 5 : the c a t a l y s t s covered with copper are p e r f e c t l y s t a b l e . I t i s hardly p o s s i b l e t o a s c r i b e the somewhat higher a c t i v i t y l e v e l of c a t a l y s t A t o an e l e c t r o n i c e f f e c t a s , a p a r t from t h e fact t h a t t h e e l e c t r o n t r a n s f e r from ruthenium t o copper i s very small (see Ref. [ 1 1 ] ) , t h e copper/ruthenium r a t i o a t the s u r f a c e i s 0.11 and an e l e c t r o n i c e f f e c t would be o p e r a t i v e a t a d i s t a n c e of a t most one atomic s t e p . The following e x p l a n a t i o n i s more l i k e l y . From the very s t a r t of the r e a c t i o n , s t r o n g l y adsorbed by-products cannot be formed on c a t a l y s t A (ensemble s i z e e f f e c t ) , c o n t r a r y t o t h e s i t u a t i o n on the s u r f a c e of a monometallic ruthenium c a t a l y s t . This then means t h a t the somewhat higher a c t i v i t y l e v e l of c a t a l y s t A i s i n fact the a c t i v i t y l e v e l of a r e a l l y pure ruthenium s u r f a c e . TABLE 3 Reaction o r d e r s i n t h e hydrogenation of benzene over c a t a l y s t s A and B and over the r e f e r e n c e c a t a l y s t 0.5 wt$ R u - o n - s i l i c a [ 1 ] . Total p r e s s u r e 130 kPa, space v e l o c i t y over c a t a l y s t A: 5.6x10 3 - 2 - 1 1 cm (STP).m Ru.h , space v e l o c i t y over c a t a l y s t B: 1.6x10 3 -2 -1 cm (STP).m Ru.h . Total p r e s s u r e was reached in each case by adding helium. catalyst temperature (K) order in

V."

order in H ?

A A B B
reference reference

303 100 303 100 303 100

-0.2

0.3
-0.1

1.1 2.2 0.3 1.5 1.2 2.1

0.6 0.0 0.2

a) w i t h i n the range of benzene p r e s s u r e s from 1.9 t o 7.9 kPa and a t a hydrogen p r e s s u r e of 79 kPa. b) w i t h i n the range of hydrogen p r e s s u r e s from 13 t o 89 kPa and a t a benzene p r e s s u r e of 5 kPa.

66
Next the question arises why the turn-over number found for catalyst B is 2.5 times as low as for catalyst A. We speculate this to be due to the dissociative chemlsorptlon of hydrogen being hampered by the very small size of the ruthenium ensembles on catalyst B, by which hampering the rate of chemiaorptlon is slowed down. According to Shimizu, Christmann and Ertl [19] ensembles of up to 5-10 adjacent ruthenium atoms are involved in dissociative hydrogen chemlsorptlon.

1000 /T (K"1) reference Ru sample 2.4 L8 3.2

- -8

- -10 In k (molecules CgHg. site'Us"1, divided by [pC6H6laxtpH2lP' Ink reference ~'2 Ru sample

2.5 2.9 1000/T (K"1)

FIGURE 6 Arrhenius p l o t s of benzene hydrogenatlon over c a t a l y s t s A and B and over the r e f e r e n c e c a t a l y s t 0.5 wt$ R u - o n - s i l i c a . Total p r e s s u r e 130 kPa, hydrogen p r e s s u r e 62 kPa, benzene p r e s s u r e 6 kPa, helium p r e s s u r e 62 kPa, space v e l o c i t y over c a t a l y s t A: 1.5X1014 cm (STP).m Ru.h" and space v e l o c i t y over c a t a l y s t B: 2.2X1014 3 -2 -1 cm (STP).m Ru.h . a i s the v a r i a b l e order in benzene and B i s the v a r i a b l e order i n hydrogen. Curve A i s measured over c a t a l y s t A, curve B i s measured over c a t a l y s t B and curve Ru/SiO i s measured over the r e f e r e n c e c a t a l y s t . All r a t e c o n s t a n t s have been c a l c u l a t e d per f r e e ruthenium s i t e .

67 4.3.1 Kinetics of the hydrogenation of benzene Reaction orders in benzene and in hydrogen were determined at 303 and at 100 K in exactly the same way as described for the case of ruthenium and copper catalysts [1,2]. Results are given in Table 3> Further experimental conditions are mentioned in the legend to the Table. The results for pure Ru-on-sillca are added as a reference. In view of the small pressure ranges of benzene and of hydrogen the accuracy of the orders-is relatively low. The results for catalyst A are very near to those for silica-supported pure ruthenium. It follows that the kinetics are not strongly influenced by the low copper coverage on the ruthenium component of catalyst A. For catalyst B the results deviate significantly from the results obtained with the reference sample and with catalyst A, especially with respect to the order in hydrogen. A direct explanation is not at hand, but this phenomenon might be due to hampering of the dissociative hydrogen chemisorption on the very small ruthenium ensembles on catalyst B. In Fig. 6 an Arrhenius plot is presented for benzene hydrogenation over catalysts A and B; results for the reference catalyst are included. It is seen that, apart from the level of activity the. course of the apparent activation energy in the case of catalyst A is about equal to the course observed for the reference sample. This last course is explained in Ref. [1]. We conclude that, just as was the case for the reaction orders, the behaviour of catalyst A with respect to the gradual change of the apparent activation energy does not deviate appreciably from the behaviour of the reference monometallic ruthenium catalyst. On the other hand, the deviation of sample B is appreciable, just as found for the orders in benzene and hydrogen.

1.1 CONCLUSIONS A n a t t r a c t i v e method of covering ruthenium catalysts with pre-chosen quantities of copper atoms has been developed. In t h i s way a high c a t a l y t i c s t a b i l i t y (increase of life-time) of the c a t a l y s t i s achieved, without an appreciable change of a c t i v i t y per ruthenium s i t e . I t i s to be recommended to choose a low copper coverage; higher coverages have a beneficial effect

68
as well, but the decrease in activity per unit weight of catalyst is unnecessarily high and the kinetics start to deviate strongly from the behaviour of ruthenium. The stabilizing action of copper and its influence on the kinetics can be explained on the basis of the ensemble size effect theory. According to Helms and Sinfelt [16] no direct evidence of an electron transfer from ruthenium to copper is found from the copper XPS core level binding energy in ruthenium-copper catalysts. We arrived at the same result, except for the case of low copper coverage. This may be accounted for by the strong chemisorptive ruthenium-copper interaction at low coverage, together with the absence of copper-copper interaction. This is in accordance with the work function results published by Christmann c.s. [11]. A significant influence of the very weak electronic effect on the catalytic performance is not observed.

ACKNOWLEDGEMENTS We thank Mr. A. P. Pijpers and Mr. J. Cremers (Department of Physical Chemistry, Central Laboratories, DSM, Geleen, The Netherlands) for carrying out the XPS/AES analyses. We also wish to thank Mr. A. Pijpers, from the same department, for the TEM micrographs. Thanks are due to Mr. J. Teunisse and Mr. N. van Westen, from Delft University of Technology, for assistance in the study of the texture of the catalysts. The investigations were supported (partly) by The Netherlands Foundation for Chemical Research (SON) with financial aid from The Netherlands Organization for the Advancement of Pure Research (ZWO).

REFERENCES 1 M.C. Schoenmaker -Stol k, J.W. Verwijs, J.A. Don and J.J.F. Scholten, accepted for publication in Appl. Catal. 2 M.C. Schoenmaker-Stolk, J.W. Verwijs and J.J.F. Scholten, accepted for publication in Appl. Catal.

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3 P.J. v.d. Steen and J.J.F. Scholten, "Proceedings of the 8th International Congres on Catalysis", Berlin, Verlag Weinheim, 1984, vol. II, p. 659. 4 V. Ponec, Adv. Catal., 32 (1983) 149. 5 C. Hoang-Van, G. Tournier and S.J. Teichner, J. Catal., 86 (1984) 210. 6 E.G. Allison and G.C. Bond, Catal. Rev., 7 (1972) 233. 7 W.A.A. v. Barneveld and V. Ponec, Rev. Trav. Chim., 93 (1974) 243. 8 G.A. Martin and J.A. Dalmon, J. Catal., 75 (1982) 233. 9 G.C. Bond, "Catalysis by Metals", Academie Press, London, 1962, p. 321. 10 S.Y. Lai and J.C. Vickerman, J. Catal., 90 (1984) 337. 11 A.J. Rouco, G.L. Haller, J.A. Oliver and C. Kemball, J. Catal., 84 (1983) 297. 12 J.H. Sinfelt, "Bimetallic Catalysts: Discoveries, Concepts and Applications", John Wiley, New York, 1983, p. 55-58. 13 M. Hansen, "Constitution of Binary Alloys", Mc Graw-Hill, New York, 1958, p. 620. 14 K. Christmann, G. Ertl and H. Shimizu, Thin Solid Films, 57 (1979) 247. 15 W.M.H. Sachtler, Disc. Faraday Soc, 72 (1982) 7. 16 R.C. Helms and J.H. Sinfelt, Surf. Sci., 72 (1978) 229. 17 J.A. Don and J.J.F. Scholten, Faraday Discuss. (Chem. S o c ) , 72 (1982) 145. 18 Y.W. Chen, H.I. Wang and J.G. Goodwin Jr., J. Catal., 83 (1983) 415. 19 H. Shimizu, K. Christmann and G. Ertl, J. Catal., 61 (1980) 412.

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SUMMARY In the chemical industry large quantities of benzene are hydrogenated to cyclohexane, an important intermediate in the production of e-caprolactam, the monomer of Nylon 6. However, a less expensive route to e-caprolactam should run via cyclohexene as an intermediate, as in this case the hydrogen consumption is reduced considerably. Research carried out in the Laboratory for Chemical Technology, Delft University of Technology, has shown that in the heterogeneous catalytic hydrogenation of benzene over ruthenium and platinum catalysts appreciable quantities of cyclohexene may be formed, provided a so-called reaction modifier is added to the feed of the reactor. Successful modifiers are substances like water, diethylene glycol and e-caprolactam. Modifiers act as scavengers through the formation of an adduct with cyclohexene, by which the adsorptive interaction of cyclohexene with the metal surface is weakened and further hydrogenation of cyclohexene to cyclohexane is hampered. This may result in an increase of the cyclohexene selectivity from nearly zero to 10 per cent or higher. A detailed report on the catalytic production of cyclohexene, followed by the conversion of cyclohexene to cyclohexanone, can be found in the forthcoming thesis by P.J. van der Steen, Delft University of Technology. It is the aim of the work described in the present thesis to support the investigations mentioned above, by studying the kinetics and mechanism of the catalytic hydrogenation of benzene over silica-supported ruthenium, copper and ruthenium-copper catalysts. In Chapter 2 the kinetics of benzene hydrogenation over a wellcharacterized ruthenium-on-silica catalyst is presented, together with the kinetics of the hydrogenation of the reaction intermediates, 1,1-cyclohexadiene and cyclohexene. Among the mechanisms proposed in the literature, the step-wise addition of adsorbed hydrogen atoms to adsorbed benzene molecules has been shown the most likely one. Evidence has been presented by us that at low temperatures, around 300 K, the addition of adsorbed hydrogen atoms to adsorbed benzene is the rate determining step. However, as a consequence of the strongly diminishing coverage of cyclohexene on

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Increasing the temperature above 300 K, the addition of hydrogen- atoms to adsorbed cyclohexene becomes rate determining. For the case of ruthenium as a catalyst a diagram has been constructed which represents the change of the free enthalpy as a function of the extension of the reaction. The positions of the free enthalpy levels of the reactants, the reaction intermediates and the products, are in accordance with the proposed mechanism, with a shift of the rate determining step above about 300 K. Chapter 3 deals with the catalytic hydrogenatlon of benzene over copper catalysts. Copper is known to be a mild hydrogenatlon catalyst, hardly able to catalyse the hydrogenatlon of the aromates. On the one side this is due to the dissociative chemisorption of hydrogen to be limited to the high Miller-index planes of copper and on the other hand to the very weak interaction of the aromatic nucleus with the surface of copper. On account of this we studied the kinetics over catalysts with a high free-copper surface area, containing very small copper crystallites. Such crystallites expose a relatively large percentage of high Miller-index planes. The reaction mechanism of benzene hydrogenatlon over copper catalysts appeared to be the same as over ruthenium catalysts, but the activity per copper site was found to be much lower than the activity per ruthenium site. On the other hand, copper has the advantage of a high catalytic stability, as contrasted with ruthenium, which deactivates fast. Tanaka-Tamaru plots (volcano curves) have been constructed, describing the rate of the hydrogenatlon of benzene over several transition metals as a function of the degree of d-orbital filling of these metals. In Chapter 4 the catalytic performance of bimetallic silica-supported ruthenium-copper catalysts is discussed. In such catalysts the advantages of ruthenium and of copper are combined; they exhibit a high activity per free ruthenium site and a high stability as well. A new technique is introduced for covering the ruthenium part of the catalyst with a pre-chosen amount of copper atoms, viz. by the reductive deposition of copper. XPS/AES spectra of ruthenium catalysts with low copper coverage (ca. 0.1) show a chemical shift in the copper peak positions, pointing to electron

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transfer from ruthenium to copper. As a consequence of the lateral coppercopper interaction, such chemical shifts are not observed at higher copper coverages (ca. 0.7). No Indications are found for the electron transfer having a significant influence on the catalytic activity. The kinetics of the hydrogenation of benzene with ruthenium catalysts, covered with a low amount of copper, is found practically equal to the kinetics with monometallic ruthenium catalysts. However, at high copper coverage, a change in the kinetics is observed with respect to the orders in hydrogen and in benzene pressure. This may be explained from the small size of the ruthenium ensembles, which hampers both the dissociative chemisorption of hydrogen and the chemisorption of benzene.

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SAMENVATTING In de chemische industrie wordt benzeen op grote schaal gehydrogeneerd tot cyclohexaan, een tussenproduct in de fabricage van e-caprolactam,het monomeer van Nylon 6. Een goedkopere procesroute naar e-caprolactam, die resulteert in de besparing in het waterstofverbruik, zou onder andere bereikt kunnen worden wanneer benzeen partieel gehydrogeneerd kan worden tot cyclohexeen. Onderzoek aan deze laatste processtap in het Laboratorium voor Chemische Technologie van de Technische Universiteit Delft, heeft uitgewezen dat, in de heterogeen-katalytische gasfasereactie over ruthenium- en platinakatalysatoren, cyclohexeen alleen in aanzienlijke mate wordt gevormd indien een modlflcator aan de voeding van de reactor wordt toegevoegd. Zo'n modlflcator, bijvoorbeeld water, diethyleenglycol of e-caprolactam, verzwakt via adductvorming de adsorptie van het cyelohexeenmolecuul op het katalysatoroppervlak en bemoeilijkt ddrhydrogenerlng tot cyclohexaan, waardoor de selectiviteit voor cyclohexeen toeneemt. Een gedetailleerd onderzoek van de katalytische bereiding van cyclohexeen, gevolgd door omzetting van cyclohexeen in cyclohexanon, is. te vinden in het binnenkort te verwachten proefschrift van P.J. van der Steen, T.U.D. Ter ondersteuning van het onderzoek naar de katalytische partile hydrogenering van benzeen tot cyclohexeen hebben wij een poging gedaan het reactiemechanisme van de katalytische benzeenhydrogenerlng verder op te helderen. De vele publicaties over dit reactiemechanisme vertonen namelijk weinig overeenstemming. Aan de hand van kinetiekmetingen aan de hydrogenering van benzeen, doch tevens van de veronderstelde reactie-intermediair en 1,4-cyclohexadl'en en cyclohexeen, over een goed gekarakteriseerde ruthenium-op-silica katalysator, hebben wij in hoofdstuk 2 een reactiemechanisme voorgesteld, dat berust op stapsgewijze additie van geadsorbeerde waterstofatomen aan geadsorbeerd benzeen. In dit mechanisme is de hydrogenering van benzeen met waterstof tot 1,1-cyclohexadi'en snelheidsbepalend bij lage temperaturen (rond 300 K ) . Bij stijging van de temperatuur verschuift de snelheidsbepalende stap naar de hydrogenering van cyclohexeen tot

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cyclohexaan, tengevolge van de snelle afname van de bezettingsgraad van cyclohexeen aan het katalysatoroppervlak. De aannemelijkheid van het voorgestelde mechanisme wordt ondersteund door berekening van een diagram dat het verloop van de reactie-vrije-enthalpie als functie van de vorderingsgraad van de reactie voorstelt voor het geval van ruthenium als katalysator. In de literatuur staat koper bekend als een milde hydrogeneringskatalysator, nauwelijks in staat om aromaten te hydrogeneren, onder andere tengevolge van het geringe vermogen van koper om waterstof dissociatief te adsorberen. Uit recente onderzoeken blijkt echter dat vooral kopervlakken met hoge Miller-indices waterstof wel dissociatief kunnen binden. Naar aanleiding hiervan hebben wij gedragen kleine koperkrlstallietjes getest in de benzeenhydrogenering (hoofdstuk 3 ) . Hiertoe zijn twee verschillende katalysatoren volgens verschillende patenten bereid en goed gekarakteri seerd. Zoals uit door ons berekende gemodificeerde Tanaka-Tamaru curven voor de hydrogenering van benzeen blijkt is de activiteit van koper zeer laag, terwijl ruthenium zeer actief is. Een voordeel van de koperkatalysatoren is echter de hoge katalytische stabiliteit, ook weer in tegenstelling tot ruthenium dat snel deactiveert (hoofdstuk 2 ) . Voor de reactie over beide katalysatoren veronderstellen wij hetzelfe mechanisme.

De bimetallische ruthenium-koperkatalysatoren, beschreven in hoofdstuk 4, verenigen in zich de goede eigenschappen van ruthenium (hoge activiteit) en van koper (hoge stabiliteit). Een nieuwe bereidingswijze voor bimetallische katalysatoren, namelijk het reductief afzetten van koper op rutheen, is in dit hoofdstuk beschreven, evenals de resultaten van de karakterisering van de katalysatoren. XPS/AES spectra tonen aan dat er bij een lage koperbezetting van het rutheniumoppervlak sprake is van een "chemical shift" van de posities van de koperpieken. Dit zou een gevolg kunnen zijn van een geringe electronenoverdracht van ruthenium aan koper. Bij hogere koperbezettingen is dit effect niet meer waarneembaar tengevolge van koper-koperinteractie. Uit de benzeenhydrogeneringsexperimenten over bimetallische katalysatoren blijkt dat koper een stabiliserend effect heeft op de

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rutheenkatalysatoren,zonder de a c t i v i t e i t per oppervlakte-rutheniumatoom nadelig t e benvloeden. Bij lage koperbezetting i s de kinetlek van de benzeenhydrogenerlng over rutheen-koperkatalysatoren vrijwel gelijk aan de klnetiek over een rutheenkatalysator. Bij hoge koperbezettingen gaat de klnetiek echter een afwijkend gedrag vertonen tengevolge van de geringe afmetingen van de ruthenium-ensembles.

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NAWOORD De velen die hebben geholpen bij de totstandkoming van dit proefschrift wil ik graag heel hartelijk bedanken. In het bijzonder wil ik noemen: - prof. dr. J.J.F. Scholten, mijn promotor, die met groot enthousiasme mijn onderzoek heeft gevolgd en de resultaten met mij heeft bediscussieerd. - de afstudeerder ir. J.W. Verwijs en de studenten-praktikanten voor de prettige samenwerking en hun eigen inbreng. - mijn collega's voor de gezellige en soms leerzame gesprekken. - de heren J. Teunisse en N. van Westen voor de hulp bij onder andere textuurmetingen en voor alle gezelligheid die zij mij deze vier Jaar hebben geboden. - medewerkers van de servicegroepen en diensten van het Gebouw voor Scheikunde in het algemeen, en van het Laboratorium voor Chemische Technologie in het bijzonder. - van het Centraal Laboratorium van DSM te Geleen voor ondersteunende analytische research: mevrouw dr. M.J. Luys en de heren J. Cremers, A. Hustings, P. v. Oeffelt, A. Pijpers en A.P. Pijpers. - de heren J.J.B. v. Holst en F. Hammers voor het verzorgen van de figuren in dit proefschrift.

77 CURRICULUM VITAE Martlne Caroline Stolk werd op 12 april 1959 te Dieraen geboren. Zij volgde kleuter- en basisonderwijs op de Montessorischool in Laren (N.H.). In juni 1977 behaalde zij haar Gymnasium-B diploma aan het Goois Lyceum in Bussum, waarna zij Scheikunde ging studeren aan de Rijksuniversiteit Utrecht. Deze studie voltooide ze in september 1982, nadat ze haar hoofdvak Anorganische Chemie, onder leiding van prof. ir. J.W. Geus, en haar bijvak Geochemie had afgerond. In november 1982 trad zij in tijdelijke dienst van ZWO/SON en werd zij in staat gesteld om dit promotieonderzoek te verrichten aan de Technische Universiteit Delft, binnen de vakgroep Chemische Technologie, onder leiding van prof. dr. J.J.F. Scholten. In oktober 1986 trad zij in dienst bij DOW Chemical (Nederland) B.V. te Terneuzen.

Stellingen bij het proefschrift "Kinetics and Mechanism of Benzene Hydrogenation over Supported Ru, Cu and Ru-Cu Catalysts". M.C. Schoenmaker-Stolk, 9 december 1986.

1 A. Sayari c.s. stellen dat zwak gebonden waterstof alleen op B5 sites kan voorkomen. Dit zou volgen uit een door deze auteurs gevonden maximum in de hoeveelheid zwak gebonden waterstof op rutheniumdeeltjes met een gemiddelde diameter van 1,1 nm. Don c.s. hebben echter op laagoppervlakkige rutheniumpoeders ook een grote hoeveelheid zwak gebonden waterstof waargenomen. Hierdoor wordt de conclusie van Sayari c.s. afgezwakt. A. Sayari, H.T. Wang en J.G. Goodwin Jr., J. Catal., 93 (1985) 368. J.A. Don, A.P. Pijpers en J.J.F. Scholten, J. Catal., 80 (1983) 296. 2 In zijn artikel over de interactie tussen katalysator en substraat in verschillende katalytische reacties, houdt Rooney geen rekening met het feit dat bij hogere temperaturen sterk gebonden substraten ook actief worden. De katalytische activiteit van een substraat is immers afhankelijk van de waarde van -AH/RT, waarin AH de adsorptiewarmte is, R de gasconstante en T de absolute temperatuur. J.J. Rooney, J. Molec. Catal., 31 (1985) 117. 3 K. Hwai-Der Liu c.s. houden in hun mechanistische beschouwingen over de Wacker-oxidatie van etheen tot ethanal, over palladiumsulfaat op een actieve kool als katalysator, ten onrechte geen rekening met de aanwezigheid van chinongroepen op het kooloppervlak. Deze groepen kunnen als chinon/hydrochinon redoxkoppel als co-katalysator werkzaam zijn. K. Hwai-Der Liu, K. Fujimoto en T. Kunugi, Ind. Eng. Chem. Prod. Res. Develop., 16 (1977) 223.

4 Het feit dat wij, onder bepaalde experimentele condities, hebben gevonden dat in de hydrogenering van 1, 4-cyclohexadi'en de cyclohexeenopbrengst groter is dan de opbrengst aan cyclohxaan, laat zien dat de resultaten van Tetenyi en Paal niet hoeven te leiden tot hun conclusie dat er bij 'de katalytische hydrogenering van benzeen een "direct" hydrogeneringsmechanisme bestaat waarbij geadsorbeerd benzeen in een stap zes geadsorbeerde waterstofatomen opneemt. Dit proefschrift, hoofdstuk 2. P. Tetenyi en Z. Paal, Z. Phys. Chem. Neue Volge, 80 (1972) 63. 5 Bij de katalytische hydrogenering van benzeen is, om thermodynamische redenen, de kans op een hoge selectiviteit voor cyclohexeen groter voor een reactie aan de fasegrens vloeistof/vast, dan voor een reactie aan de fasegrens gas/vast. J.A. Don, dissertatie Technische Hogeschool Delft, 1981. J.A. Don en J.J.F. Scholten, Faraday Discuss. (Chem. S o c ) , 72 (1977)
145. . . . . , . . . .

6 Bij de dehydrogenering van cyclohxaan vindt Sinfelt nauwelijks verandering in de katalytische activiteit.wanneer hij koper-toevoegt aan een nikkel katalysator. Bij een poging tot verklaring'van dit verschijnsel heeft hij over het hoofd gezien dat koper evenals nikkel een grote activiteit heeft voor dehydrogeneringsreacties als de cyclohexaandehydrogenering.

J.H. Sinfelt, Ace. Chem. Res., 10 (1977) 15. R. Pearce en W.R. Patterson, "Catalysis and Chemical Processes", Leonard Hill, Glasgow, 1981, p. 265, 274, 318-319.

7 De titel van het boek van Somorjai: "Chemistry in Two Dimensions: Surfaces", kan aanleiding geven tot misverstanden. "Multidimensional Chemistry: Surfaces" zou meer recht doen aan onderwerp en inhoud van het boek.

G.A. Somorjai, "Chemistry in Two Dimensions: Surfaces", uitgave: Cornell University Press, Ithaca-London, 1981. 8 Het is merkwaardig dat in de Oosthoek-Times Wereldatlas, hoofdstuk "Nuttige Delfstoffen", bij het element platina wordt vermeld dat dit metaal "een katalytische werking heeft", maar niet bij elementen als nikkel, koper, cobalt en zilver. Oosthoek-Times Wereldatlas, * 4 e druk, uitgave Kluwer Algemene Boeken b.v., Wageningen, 1977, p. 16. 9 De patrouillerende gemotoriseerde politie op onze autosnelwegen kan gevaarlijke situaties oproepen doordat weggebruikers plotseling snelheid veranderen op het moment dat zij zich bewust worden van de politile aanwezigheid. 10 Na de moderniseringen van de veehouderijen in Nederland, die de laatste tien jaar zijn ingevoerd, loopt de koe los en zit de boer vast.