Reac Kinet Mech Cat (2010) 100:99103 DOI 10.

1007/s11144-010-0164-4

Highly selective hydrodechlorination of CCl4 into CHCl3 on AgPd/carbon catalysts

Mohong Lu Jianzhi Sun Dongbao Zhang Mingshi Li Jianjun Zhu Yuhua Shan

Received: 11 December 2009 / Accepted: 30 January 2010 / Published online: 17 February 2010 Akademiai Kiado, Budapest, Hungary 2010

Abstract A series of AgPd/C catalysts with different Ag/Pd molar ratios were prepared by impregnation and characterized by N2 adsorption and XPS. The catalytic performance was investigated in the hydrodechlorination of carbon tetrachloride into chloroform. High selectivity toward chloroform, near 100%, was obtained over AgPd/C bi-metal catalysts. A very pronounced surface enrichment with Ag in AgPd/C catalysts determined by XPS may be responsible for the high selectivity of chloroform. It is suggested that hydrodechlorination of carbon tetrachloride into chloroform occurs on the surface of Ag in the AgPd alloy and the role of Pd is to supply H atoms necessary. Keywords Carbon tetrachloride Hydrodechlorination Chloroform Selectivity AgPd

Introduction The use of carbon tetrachloride (CCl4) has been phased out together with chlorouorocarbans (CFCs) in developed countries according to the Montreal Protocol effective as of 1 January 1996, due to its potency in depleting the stratospheric ozone layer. The elimination of CCl4 by combustion is an expensive and polluting process. An attractive way to eliminate CCl4 is to convert it into chloroform (CHCl3), which is a valuable intermediate product in organic synthesis, by catalytic hydrodechlorination. The catalysts employed widely for this reaction
M. Lu J. Sun D. Zhang M. Li (&) J. Zhu Y. Shan Key Laboratory of Fine Petrpchemicals, Department of Chemical Engineering, Jiangsu Polytechnic University, Changzhou 213164, Peoples Republic of China e-mail: mingshili@yahoo.com M. Lu Changzhou Mesoporous Catalytic Material Ltd, Changzhou 213164, Peoples Republic of China

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are noble metals such as Pd and Pt [17]. Although the formation of chloroform is the most favored process in the hydrodechlorination of carbon tetrachloride on noble metal catalysts [4], the selectivity of chloroform is lowered due to the formation of subsequent hydrodechlorination products such as methane. The modication of Pt and Pd catalysts by the addition of a second metal may dramatically change the activity and selectivity of many reactions. Several studies on the hydrodechlorination of 1,2-dichloroethane demonstrated that the addition of Ag to Pd can strongly suppress further hydrogenation of ethylene and increase the selectivity of ethylene [810]. The present authors prepared a series of AgPd bi-metal catalysts and measured the catalytic performance of AgPd/C catalysts in the hydrodechlorination of CCl4 into CHCl3. The purpose of the present study is to investigate the inuence of Ag addition to Pd on the hydrodechlorination of CCl4 and to discuss the role of Ag in the bi-metal catalysts.

Experimental The AgPd/C catalysts were prepared by the successive impregnation method. Activated carbon was rst added to an aqueous H2PdCl4 solution and dried at 393 K. The samples obtained were impregnated with the aqueous solution of AgNO3 (AR). The Pd/C catalyst was prepared by incipient wetness impregnation of H2PdCl4 solution onto activated carbon. The loading of palladium in all the Pd/C and AgPd/C catalysts was kept at 1 wt%, while the atomic ratios of Ag to Pd were 1:1, 2:1 and 4:1. The catalysts were dried overnight at room temperature, further dried at 393 K for 12 h, and then reduced at 623 K in a 20 mL min-1 ow of H2 for 2 h. Nitrogen adsorption was measured with an ASAP 2400, which reports adsorption isotherm and BET specic surface area automatically. X-ray photoelectron spectroscopy (XPS) measurements were carried out using a Multilab2000 X-ray photoelectron spectrometer. MgKa was used as the photon source. For the individual energy regions, the pass energy of 20 eV was used. All XPS spectra were corrected to the C1s peak at 284.6 eV. The catalytic activity measurements were performed in an autoclave reactor at 4 MPa, and 398 K. In order to maintain the reactor pressure constant, the hydrogen was supplied continuously to the reactor at the rate it was consumed by the reaction. For each run, 2 mL CCl4 in 28 mL n-heptane, with 0.6 g of the powdered catalyst in suspension, was charged in the reactor. Prior to the start of each catalytic experiment, the reactor was purged by H2, and then heated to the reaction temperature. Liquid samples and methane in gas samples were collected at interval of 1 h and analyzed by a Varian CP-3800 gas chromatograph.

Results and Discussion The BET surface area and the relative surface Ag/Pd atomic ratios determined by XPS of the four catalysts are listed in Table 1. The surface area of catalysts is

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Highly selective hydrodechlorination of CCl4 into CHCl3 Table 1 BET surface area and Ag/Pd molar ratio of catalysts

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Catalysts

SBET/(m2 g-1)

n(Ag)/n(Pd) na XPSb 0 2.24 3.91 7.88

Pd/C
a

878 867 878 833

0 1 2 4

n is the nominal Ag/Pd molar ratio

AgPd/C (1:1) AgPd/C (2:1) AgPd/C (4:1)

XPS is the Ag/Pd molar ratio determined by XPS

slightly changed by the addition of Ag because of a small metal loading over the supports. And it is clear that the surface Ag/Pd atomic ratios of AgPd/C catalysts are much higher than the corresponding nominal values, suggesting a very marked enrichment in silver for AgPd alloy surface. This is in agreement with the results obtained by Heinrichs according to CO chemisorption, XRD and TEM [11]. The effect of Ag addition to the Pd/C catalysts on the activity in the hydrodechlorination of CCl4 was investigated. Fig. 1 shows the conversion of CCl4 as a function of time on Pd/C and AgPd/C catalysts. It suggests that the conversion of CCl4 is inuenced substantially by Ag adding. For AgPd(1:1)/C catalyst, the conversion of CCl4 is dramatically lowered by adding Ag to Pd. However, the conversion of CCl4 increases with an increase in the Ag content. Especially, the activity of AgPd(2:1)/C and AgPd(4:1)/C is comparable with that of Pd/C. According to the relative surface Ag/Pd atomic ratios of Pd/C and AgPd/C catalysts determined by XPS (Table 1), Ag was mainly located on the surface of AgPd alloy particles. The results obtained by Heinrichs by means of CO chemisorption, XRD and TEM show a very pronounced surface enrichment of Ag in the AgPd alloy [11]. Our previous study [12] suggested that the saturation coverage of H2 adsorption decreases with an increase in the Ag/Pd atomic ratio, which may be caused by blocking of some Pd surface by Ag. Therefore, the number of sites for CCl4 adsorption on the surface of Pd decreases when the Ag content increases. However, increasing silver content in the AgPd bi-metallic catalysts results in an increase in CCl4 conversion. So it is reasonable to suppose that CCl4 is adsorbed on Ag sites at the surface of AgPd particles and then CCl bond scission
Fig. 1 The conversion of carbon tetrachloride over four catalysts as a function of time. (open square) Pd/C; (closed circle) AgPd(1:1)/C; (closed triangle) AgPd(2:1)/C; (closed star)AgPd(4:1)/C

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Conversion / %

80 60 40 20 0

10

Time / h

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occurs. Fung and Sinfelt [13] reported that Ag is able to adsorb the chlorinated molecules such as CH3Cl and break the CCl bond. According to the study of Heinrichs concerning the hydrodechlorination of 1,2-dichloroethane on AgPd/SiO2 [8], dechlorination of 1,2-dichloroethane into ethylene occurs on silver through dissociative adsorption with successive breaking of two CCl bonds. Therefore, silver sites at the surface of AgPd particles are responsible for the CCl4 conversion. The increasing conversion of CCl4 is attributed to an increase in silver content due to the formation of more active sites at the AgPd alloy surface. Fig. 2 shows the product distribution on AgPd/C and Pd/C catalysts obtained at 6 h. Chloroform is the major product on Pd/C catalyst, which is in agreement with the results obtained by Sainero et al. [5]. Some methane and dichloromethane as successive hydrodechlorination products are also observed, which lead to the decrease in selectivity of chloroform. However, for the AgPd/C catalysts, the selectivity of chloroform is up to about 98%, especially the selectivity close to 100% is obtained on AgPd(2:1)/C catalyst, which is much higher than that for Pd/C catalyst. The formation of methane and dichloromethane is almost completely suppressed by the addition of Ag. It is worth noting that the selectivity of chloroform is little inuenced by the content of Ag (Fig. 1), although a remarkable change to the conversion of CCl4 is observed. We should keep in mind that hydrodechlorination CCl4 of occurs on Ag from the previous discussion about Fig. 1. It is indicated that the formation of chloroform is more favored on Ag than on Pd maybe due to the lower concentration of activated H on the surface of Ag. The activated H atom on Ag, which is unable to activate H2 by itself, is supplied by Pd on the surface of alloy. Heinrichs reported that Pd presented on the surface of AgPd alloy can supply H atom through hydrogen dissociative chemisorption to regenerate of chlorinated silver surface into metallic silver [8]. For pure palladium catalysts, it seems reasonable to assume that CCl4 is adsorbed on Pd sites, successive CCl breakage and interaction with H atoms could take place to form dichloromethane and methane because of sufcient activated H atoms supplied by Pd. However, for AgPd catalysts, breaking of CCl occurs on Ag, and the amount of activated H atoms necessary supplied by Pd is lowered due to blocking of some
Fig. 2 The product distribution over four catalysts at 6 h

60 40 20

C 1)/ (4: /C Pd (2:1) C Ag -Pd 1)/ g (1: /C A d -P Pd Ag

Dic Me tha ne

0 Ch lor o

hlo

for

rom

eth

ane

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Selectivity /%

100 80

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Pd surface by Ag (Table 1). So suppression of further dechlorination of CCl3 fragment results in high selectivity for chloroform. It is worth noting that there were some differences between the results here and those obtained by the group of Heinrichs in several studies on the hydrodechlorination of 1,2-dichloroethane [8 10]. In their works, 1,2-dichloroethane was completely dechlorinated and hydrogenated to ethane over non-doped Pd, whereas the reaction stopped at ethene in the presence of silver. Therefore, all chlorine from 1,2-dichloroethane was stripped off on Ag active sites. Here, we propose that silver sites are able to remove only one Cl atom from the molecule of CCl4. According the discussion above, a reasonable mechanism is proposed that hydrodechlorination of CCl4 into chloroform occurs on Ag through dissociative adsorption with breaking of CCl followed by the interaction with two H atoms to form chloroform and hydrogen chloride and regenerate the active sites. The role of Pd in the alloy is to supply the H atoms necessary through dissociative adsorption of hydrogen.

Conclusions In summary, the activity and selectivity of AgPd/C in hydrodechlorination of carbon tetrachloride into chloroform in liquid phase was studied in order to investigate the role played by Ag in the AgPd alloy. A high selectivity toward chloroform, near 100%, was obtained over the AgPd (2:1)/C catalyst, while the conversion of carbon tetrachloride was comparable with that on Pd/C catalyst. Although a remarkable change in the conversion of carbon tetrachloride was observed, the selectivity toward chloroform was hardly inuenced by the Ag content. It is reasonable to propose that hydrodechlorination of carbon tetrachloride into chloroform takes place on the surface of Ag and the H atoms necessary are supplied by Pd at the surface of the alloy.
Acknowledgments The authors thank the nancial supports from the National Natural Science Foundation of China (20976076), the Natural Science Foundation of Jiangsu Province (BK2009536).

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