J. Chem. T echnol. Biotechnol.

1998, 73, 414 420

Ching-Yeh Shiau* & J. C. Tsai

Cu/SiO Catalyst Prepared by Electroless Method 2

Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan
(Received 26 January 1998 ; accepted 5 August 1998)

Abstract : Cu/SiO catalysts prepared by an electroless deposition method were 2 investigated and compared with those by an impregnation method. Copper contents varied from 5% to 15% and SiO was used as support. All catalysts were 2 characterized by BET, DSC, SEM and TPR and tested by an n-butanol dehydrogenation reaction for activities and stabilities. BET analysis showed that the catalysts prepared by the two methods present larger average pore size and less surface area than those of the fresh SiO , indicating that smaller pores may get 2 This blockage is more severe in the blocked during the course of preparation. impregnation method. SEM photos showed that the electroless method produces smaller copper crystals than the impregnated method. The reaction activity was found to be in the order of the calcined electroless copper catalyst [ the fresh electroless copper catalyst [ impregnated copper catalyst. ( 1998 Society of Chemical Industry J. Chem. T echnol. Biotechnol. 73, 414 420 (1998) Key words : copper catalyst ; electroless plating ; impregnation ; SiO ; n-butanol 2 dehydrogenation

INTRODUCTION Copper-based catalysts are widely used in many industrial reactions, especially for dehydrogenation reactions. Church and Joshi1 and Franckaerts and Froment2 indicated that a CuCoCr catalyst had good activity for ethanol dehydrogenation. Pepe et al.3 studied the dehydrogenation of isopropanol and found that the reaction rate increased linearly with the exposed copper surface area of the supported catalysts. Doca and Segal4 h7 used Cr-, Mn-, Fe- and Ni-promoted copper catalysts to investigate the kinetics of low aliphatic alcoholic (C C ) dehydrogenation in the temperature range of 2 4 200 280C by a chromatographic pulse technique. They found that the fresh copper catalyst was very active, but its activity decreased rapidly with pulse number. If the promoters Cr and Mn were added into the catalysts, the activity of the catalysts remained fairly constant for a
* To whom correspondence should be addressed. Contract/grant sponsor : National Science Council of the Republic of China ; Contract/grant number : NSC84-2214E011-005.

longer time due to the formation of a Cu-oxide junction. Prasad et al.8 and Tu et al.9 studied the role of chromia in a copper catalyst for the dehydrogenation of ethanol ; the addition of chromia improved dispersion of copper on the support and helped to prevent the catalyst from sintering. Sivaraj et al.10 found that CuZnO Al catalysts prepared by a depositionprecipitation method had high selectivity for the dehydrogenation of cyclohexanol to cyclohexanone. Lin et al.11 used a CuZnO catalyst to investigate the oxidative dehydrogenation of cyclohexanol to cyclohexanone. Sivaraj et al.12 examined the selectivity dependence on the acidity of supported copper catalysts prepared using the urea hydrolysis procedure in the hydrogenation of cyclohexanol. Shiau and Liaw13 found that a CuBa catalyst was potentially attractive for the dehydrogenation of nbutanol to butyraldehyde. Shiau and Chen14 also found that a CuCr catalyst was quite eective for the ethanol dehydrogenation reaction. Grift et al.15 studied the eect of preparation procedure on the reduction behavior of silica-supported copper catalysts. They found that the dispersion of copper strongly depended on the preparation methods and the conditions used. 414
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( 1998 Society of Chemical Industry. J. Chem. T echnol. Biotechnol. 0268-2575/98/$17.50.

Cu/SiO catalyst prepared by electroless method 2 Traditionally, copper catalysts are prepared by either impregnation methods or precipitation methods. Recently, electroless deposition method has been adopted in the preparation of copper catalysts. Chang and Saleque16 h19 used this method to prepare a copper catalyst on Al O for the dehydrogenation reactions 2 3 and found that the catalysts prepared by the electroless method were better than those prepared by the conventional methods. Shiau and Tsai20 also found similar results for the dehydrogenation reaction of n-butanol when using Cu/Al O catalysts prepared by the electro2 3 less method. In this study, the electroless deposition method was used to prepare copper catalysts for the dehydrogenation of n-butanol. SiO was used as 2 support. All the catalysts prepared by the electroless method were compared with the catalysts prepared by the impregnation method.

415 method, E denotes electroless method and the numbers represent the copper content in the catalyst as a percentage. The copper content was determined by atomic absorption spectrometry. The catalysts were characterized by BET, DSC, SEM and TPR analyses. n-Butanol reaction The catalyst activity data were obtained by carrying out the dehydrogenation reaction of n-butanol in a continuous ow type reactor with a xed catalyst bed under atmospheric pressure. The reactor was made of a Pyrex tube with 136 mm inner diameter, equipped with a thermocouple well along the central axis. A known amount of catalyst was loaded in the reactor. Pure nbutanol was fed into the reactor by a metering pump. The reaction temperature was set at 270C. All connecting gas lines and valves were wrapped with heating tape to prevent possible condensation. The compositions of inlet and outlet streams were determined chromatographically using a column loaded with Porapak Q. The experiments were conducted under conditions free of external mass transfer and internal diusion resistances.

EXPERIMENTAL Catalyst preparation Electroless method The electroless method is an oxidationreduction chemical deposition reaction, which can deposit certain metals on a substrate without an external electrical source. In this study SiO was used as substrate. Before 2 electroless deposition, SiO was rstly treated with 2 dilute acid solution to remove any fats and oils. The clean SiO was then treated with palladium chloride 2 solution for activation. At this stage, palladium served as seeds for catalytic nucleating centers. The activated SiO was nally contacted with copper solution for 2 copper plating. In the copper solution, formaldehyde was added as reducing agent for the oxidation reduction reaction. The plating bath was maintained at 70C and the pH was varied from 11 to 13. The plated SiO was then ltered and washed with distilled water, 2 then dried at 110C for 24 h. The copper content was controlled by the plating solution concentration as well as the plating time. The plated copper catalysts can be directly used as the plated copper is present as copper atoms instead of copper oxide. However, some fresh electroless copper catalysts were also calcined at 450C for 3 h to study the calcination eect. Impregnation method Catalysts were prepared by putting SiO support into a 2 copper nitrate solution container for 30 min impregnation. The container was then placed in an isothermal water bath to vaporize most of water. The bath temperature was maintained at 70C. The soaked paste was then dried at 110C and calcined, if necessary, at 450C for 3 h. Six catalysts were prepared, namely, I05, I10, I15, E05, E10 and E15 in which I denotes impregnation

RESULTS AND DISCUSSION Catalyst characterization Table 1 shows the specic surface areas and the mean pore sizes for the six types of catalysts measured by the BET method. Fresh SiO was also included for refer2 ence. As can be seen from this table, all the catalysts have less surface area and larger mean pore size than the fresh SiO , and the catalysts prepared by the elec2 troless method exhibit a larger surface area and smaller mean pore size than all the impregnated catalysts. Moreover, the surface area increases and the mean pore size decreases with increasing copper loading for the electroless catalysts, but vice versa for the impregnated catalysts. All this information indicates that the impregnation method will block some small pores and this
TABLE 1 BET Surface Analysis Catalyst SiO2 I05 I10 I15 E05 E10 E15 Surface area (m2 g~1) 2988 2552 2415 2347 2644 2712 2785 Pore size (A ) 2113 2430 2562 2664 2385 2324 2253

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C.-Y . Shiau, J. C. T sai copper loading increases. This is due to the fact that copper was more uniformly plated on the wall of the pores by the electroless method. Expect for those ne pores which became blocked, the pore size of the nonblocked pores therefore becomes smaller when copper loading increases. Apart from the BET surface area, the copper particle size also plays an important role in the catalysts activity. Figures 3 and 4 are the SEM photos of the I15 catalyst and the fresh E15 catalyst, respectively. It is seen from these two gures that the electroless method produces quite small ball-like copper catalysts whereas the impregnated methods forms much larger needle-like ones. Thus, the crystal type is quite dierent in the two preparation methods and the copper crystal size prepared by the electroless method is much smaller than that prepared by the impregnation method. Figure 5 is the SEM photo of calcined E15 catalyst. Comparing Figs 3 and 5 shows that even the calcined E15 catalyst gives smaller crystals than the I15 catalyst. Figure 6 and 7 are the TPR proles of the six catalysts. The TPR experiments were conducted in a xed bed reactor from room temperature to 500C at a con-

Fig. 1. Pore distribution for impregnated catalysts.

blockage will become more severe with increasing copper loading, but the blockage phenomenon in the electroless method is much less. These blockage phenomena can also be seen from the pore distribution curves, as shown in Figs 1 and 2. Figure 1 is the pore distribution for the impregnation method and Fig. 2 for the electroless method. It is clearly seen from Fig. 1 that the specic pore volume was sharply decreased when loading copper metal onto the support by the impregnation method and the curves are slightly right-shifting when the copper loading increases, indicating that more smaller pores are blocked when increasing copper loadings. In contrast, the curves for the electroless method, as shown in Fig. 2, are slightly left-shifting when the

Fig. 3. SEM photo of I15 catalyst.

Fig. 2. Pore distribution for electroless catalysts.

Fig. 4. SEM photo of E15 catalyst.

Cu/SiO catalyst prepared by electroless method 2

417

Fig. 5. SEM photo of E15 catalyst with calcination.

stant rate of 10C min~1. A mixture stream of H /Ar 2 (25%/75%) was introduced at 30 cm3 min~1 to reduce the calcined catalyst sample. The effluent stream was analyzed for hydrogen by a thermal conductivity detector after removal of moisture by a molecular sieve trap. For both preparation methods ; the TPR of each catalyst exhibited only one peak. This peak is attributed to the reaction : CuO ] H ] Cu ] H O 2 2 Both gures show that larger copper loadings have larger hydrogen consumption. However, comparing the two gures indicates that the reduction pattern is slightly dierent for the two types of catalysts. Firstly, the peak maxima of the impregnated catalysts are about 50C higher than those of the electroless catalysts. Sec-

Fig. 7. TPR spectra for electroless catalysts.

Fig. 6. TPR spectra for impregnated catalysts.

ondly, the TPR curves of the electroless catalysts are much sharper and narrower than those of the impregnated catalysts. Thirdly, as can be seen from Fig. 6, there are no real peak maxima for the I05 and I10 catalysts. These three points imply that the interaction between copper and the support for the two preparation methods are dierent and the electroless catalysts are easier to get reduction. The DSC analysis traces, recorded in the temperature range of room temperature up to 450C at a rate of 10C min~1 for the impregnated and the electroless catalysts are given in Figs 8 and 9 respectively. In Fig. 8, an endothermic peak was observed around 100C, indicating the dehydration of the impregnated catalysts. Starting from 230C to about 290C, a larger endothermic peak was observed. This peak represents the decomposition of copper salts and some kind of bonding formed between copper and support. Higher copper loadings give larger peaks. Above 300C, no peaks were observed, indicating that the impregnated catalysts are quite stable from 300 to 450C. For the electroless catalysts, as shown in Fig. 9, a similar endothermic peak was observed around 100C followed by a wide exothermic peak. The endothermic peak is the vaporization of water inside the catalyst and the exothermic peak represents the phase change of fresh electroless copper to copper oxides. Again, higher copper loadings present larger peaks. No endothermic peak at around 250C was observed for the electroless catalysts, indicating that the interaction between copper and support for the electroless catalysts may be dierent from that for the impregnation catalysts. This point seems quite similar to the TPR result.

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C.-Y . Shiau, J. C. T sai

Fig. 8. DSC spectra for impregnated catalysts.

Fig. 10. Reaction activity of 5% Cu catalysts.

Catalyst activities Dehydrogenation of n-butanol is used as the test reaction for the catalysts activity. The catalysts loading was 04 g and time factor was 47 g-cat h gmole~1. Experimental results show that all the catalysts dehydrogenate n-butanol into n-butyraldehyde and hydrogen. Only a

trace amount of heavy compounds was detected. Figures 10 12 show the catalysts stabilities and activities for the n-butanol dehydrogenation reaction. The calcined electroless copper catalysts are also included. Comparing these three gures reveals three interesting points. Firstly, higher copper loadings have better reaction activities and the electroless copper catalysts

Fig. 9. DSC spectra for electroless catalysts.

Fig. 11. Reaction activity of 10% Cu catalysts.

Cu/SiO catalyst prepared by electroless method 2

419 cined electroless copper catalysts may be attributed to the interaction between copper and support during calcination. Catalyst deactivation Coking and sintering problems which cause catalyst deactivation were also investigated in this study. For the coking problem, we used elemental analysis to determine the weight % of carbon present in the catalyst after an 8 h reaction at 270C, and for the sintering problem we used the BET method to determine the surface area change. Table 2 shows the result of elemental analysis which indicates that all the catalysts have carbon deposition after undergoing the dehydrogenation reaction. The weight percentage of carbon on the copper surface ranges from 081% to 632%. Table 2 also shows that after the dehydrogenation reaction the catalysts prepared by the electroless method have much less carbon deposition than the impregnated catalysts. The amount of carbon deposition for the electroless catalysts is much less than 40% of that for impregnated ones. Table 3 compares the BET surface area between the fresh and used catalysts. The fourth column in the table is the percentage change of the surface area after reaction. As can be seen from this result, the impregnated catalysts have a signicant sintering phenomenon while the degree of sintering is slight for the electroless catalysts. The percentage decrease in surface area for the electroless catalysts is about one-fth of that for the impregnated catalysts. Tables 2 and 3 clearly indicate why the electroless catalysts show better stability and activity than the impregnated catalysts do, as aforementioned in the reaction performance results.

Fig. 12. Reaction activity of 15% Cu catalysts.

present better performance for all copper loadings. Secondly, all the impregnated catalysts are deactivated signicantly, especially the I05 catalyst. In contrast, both E10 and E15 are quite stable during an 8 h reaction course. Thirdly, the calcined electroless copper catalysts show much better reaction activities than the fresh electroless copper catalysts. The higher activities of the calTABLE 2 Carbon Content after Reaction Catalyst I05 I10 I15 E05 E10 E15 Carbon content (wt%) 632 545 498 242 114 081

CONCLUSIONS (1) All the characterization results show that the electroless deposition method provides more uniform copper distribution than the impregnation method. (2) Although the calcined electroless copper catalysts have larger copper particles, they exhibit better reaction activities than the fresh electroless catalysts. (3) The reaction activities are in the order of the calcined electroless copper catalyst [ the fresh electroless copper catalyst [ the impregnated copper catalysts.

TABLE 3 Surface Area Change after Reaction Catalyst Fresh I05 I10 I15 E05 E10 E15 2552 2415 2347 2644 2712 2785 BET surface area (m2 g~1) Used 2222 2244 2274 2581 2685 2734 % change [ 129 [ 71 [ 31 [ 24 [ 10 [ 18

ACKNOWLEDGEMENT This work was supported by the National Science Council of the Republic of China (NSC84-2214-E011005).

420 REFERENCES
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