Research Article

Received: 31 March 2010 Revised: 17 May 2010 Accepted: 17 May 2010 Published online in Wiley Online Library: 18 June 2010

(wileyonlinelibrary.com) DOI 10.1002/jctb.2456

Hydrogenolysis of glycerol to 1,2-propanediol catalyzed by Cu-H4SiW12O40/Al2O3 in liquid phase

Shun-Li Hao,a,b Wei-Cai Peng,a Ning Zhao,a Fu-Kui Xiao,a Wei Weia and Yu-Han Suna,c
Abstract
BACKGROUND: Crude glycerol will increase to over 400 million L year1 , and the market is likely to become saturated due to the limited demand for glycerol. The main aim of this work is to develop a novel process for the sustainable conversion of glycerol to 1,2-propanediol (l,2-PD). RESULTS: Cu-H4 SiW12 O40 /Al2 O3 catalysts with different H4 SiW12 O40 (STA) loadings were prepared for the hydrogenolysis of glycerol to produce l,2-PD in liquid phase. At 513 K, 6 MPa and LHSV of 0.9 h1 in 10% (w/w) glycerol aqueous solutions, the catalyst with 5% (w/w) STA showed the best performance with 90.1% of glycerol conversion and 89.7% selectivity to l,2-PD. More important, both the initial glycerol conversion and l,2-PD selectivity were maintained over 250 h. CONCLUSION: l,2-PD can be continuously produced with high yields via the liquid phase hydrogenolysis of glycerol over Cu-H4 SiW12 O40 /Al2 O3 . Furthermore, the characterization indicated that catalyst acidity could be greatly modied by STA, which promoted Cu reducibility. It was also found that hydrogenolysis could be favored by a bi-functional catalyst with the appropriate amount of both acid and metal sites. c 2010 Society of Chemical Industry Keywords: glycerol; hydrogenolysis; 1; 2-propanediol; CuH4 SiW12 O40 /Al2 O3

INTRODUCTION
1,2-propanediol, a three-carbon diol with a stereogenic site at the central carbon atom, is a non-toxic and important medium-value commodity chemical, which is widely used for polyesters and alkyd resins, pharmaceuticals, cosmetics, brake uid and humectants, and green alternatives to an ethylene glycol based toxic deicing/antifreeze agent.1 5 Nowadays, l,2-PD is produced industrially from petroleum-derived5 chemicals via the chlorohydrin or hydroperoxide processes.1,2 These are now restricted by the rapid increase in oil price and the dwindling petroleum resource, therefore the production of l,2-PD from renewable resources is highly desirable. However, with the annual world production of biodiesel expected to increase to over four billion liters by the end of this decade, the crude glycerol by-product of the process will increase to over 400 million liters per year.6 The glycerol market is likely to be saturated because of limited utilization of glycerol at present. However, glycerol is regarded as one of the building blocks in the bio-renery feedstock, and much attention has been paid recently to the conversion of glycerol to high value-added products, such as glycols and acrolein.7,8 The hydrogenolysis of glycerol has been reported in several patents9 12 and academic literature,13 31 mainly focused on the development of catalysts, such as CuO/ZnO,2,19,25 CuCr,3 Raney Ni,3,27 sulded Ru,11,23 Ru/C,2,15,17,18 or Rh/C,2,18 Pt/C,18 Rh/SiO2 +ion-exchange resin,15,17 CuPt and CuRu26 bimetallic catalysts etc. Among them, the

noble metal based catalysts appear more active than Cu based catalysts for the hydrogenolysis reaction, but the selectivity to l,2-PD is relatively lower,2,20 23,27 29 which may be due to an excessive CC bond cleavage.11,20,21 Copper-containing catalysts have exhibited excellent activity for CO bond breakage prior to CC bond breakage.20,24 However, most of these studies were performed in a stainless autoclave with discontinuous operation.30,31 This can lead to drawbacks with regard to product separation, the essential addition of organic solvents and the deactivation of catalysts. In this study, the production of 1,2PD has been carried out from glycerol aqueous solution with high selectivity over CuH4 SiW12 O40 /Al2 O3 catalysts; the catalyst exhibited high activity and selectivity with remarkable stability for the hydrogenolysis of glycerol.

Correspondence to: Wei Wei and Yu-Han Sun, State Key Laboratory of Coal conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, P.R. China. E-mail: weiwei@sxicc.ac.cn; yhsun@sxicc.ac.cn

a State Key Laboratory of Coal conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, P.R. China b Graduate School of Chinese Academy of Sciences, Beijing 100049, P.R. China

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c Low Carbon Energy Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203, P.R. China

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EXPERIMENTAL
Catalyst preparation Cu-based catalysts were prepared by incipient wetness impregnation which has been described previously.32 Typically, Al2 O3 (2040 mesh) was impregnated with the desired amount of STA aqueous solution for 24 h at room temperature, then dried at 393 K overnight and calcined at 623 K for 5 h in air. The STA/Al2 O3 samples obtained were further impregnated with an aqueous solution of Cu(NO3 )2 3H2 O at room temperature for 24 h to obtain 5% (w/w) Cu loading. After drying at 393 K, the samples were calcined in air at 623 K for 5 h. The catalysts are labelled 5Cu-xSTA/Al2 O3 , where x represents the nominal weight loading of STA. Characterization BET surface areas, pore volumes, and average pore diameters were determined by N2 adsorptiondesorption method at 77 K, measured using a Micromeritics Tristar 3000 (Particle & Surface Sciences Pty. Limited, American) instrument. The samples were degassed under vacuum at 473 K for 12 h before the measurement. The average pore diameters were calculated according to the BJH method. X-ray powder diffraction (XRD) patterns were recorded on a Rigaku Miniex (M/s. Rigaku Corporation, Japan) X-ray diffractometer using Ni ltered Cu K radiation (k = 1.5406 ) with a scan speed of 2 min1 and a scan range of 590 at 30 kV and 15 mA. Temperature programmed desorption of NH3 (NH3 -TPD) analysis was conducted using an in-house constructed apparatus. The catalyst sample (200 mg) was rst purged in Ar for 2 h at 473 K, then cooled to room temperature and NH3 adsorption was carried out by passing a 30% NH3 /Ar mixture for 1 h. Any residual NH3 was removed in a ow of dry Ar at the same temperature, the temperature was then raised to 873 K at a heating rate of 10 K min1 and the desorption of NH3 was recorded by Balzers Omnistar mass spectrometry (Balzers Inc., Switzerland) (m/z = 16 was used to avoid the inuence of water). Temperature programmed reduction (H2 -TPR) analysis was performed on a conventional apparatus with a thermal conductivity detector (TCD). 50 mg samples were loaded in a quartz tube and purged with Ar at 423 K for 60 min, and then cooled to 333 K. Reduction was carried out from 333 K up to 1073 K (10 K min1 ) in a 10% H2 /Ar mixture with a ow rate of 30 mL min1 . Catalytic evaluation The hydrogenolysis of glycerol in liquid phase was performed in a xed-bed stainless steel reactor (length 800 mm and i.d. 20 mm) with a back pressure valve to control the reaction pressure. The glycerol aqueous solution was introduced by a high-pressure pump into the reactor. Prior to reaction, the catalysts were reduced in hydrogen with a ow rate of 40 mL min1 at 573 K for 5 h. The products were analyzed by HPLC (Schimadu LC-2010Avp, Kromasil-C18, 5 , 4.6 mm 250 mm stainless steel column). Conversion of glycerol and selectivity of products were dened as follows: Conversion of glycerol (%) Sum of C mol of all liquid products 100% = Added glycerol before reaction Selectivity (%) C mol of each liquid product 100% = Sum of C mol of all liquid products

RESULTS AND DISCUSSION

Structure and texture The textural properties of a range of catalysts are presented in Table 1. Both surface area and pore volume of Al2 O3 -supported Cu-STA decreased with an increase in STA loading, indicating that some of the pores in Al2 O3 were plugged by STA. Figure 1 shows the XRD patterns of Al2 O3 impregnated with 5% (w/w) Cu at different STA loadings. All of them had similar XRD patterns, except those peaks at 32.35 , 37.63 , 39.62 , 45.52 , 60.27 and 67.01 due to the presence of -Al2 O3 . For all the catalysts, however, no diffraction lines were associated with STA, even at STA content up to 30% (w/w), indicating no formation of any mixed oxide phases. This was consistent with another report.33 Thus, Cu and STA appeared to be completely X-ray amorphous on the Al2 O3 surface. This could be due to the strong interaction between STA and Al2 O3 ,33 which possibly leads to high dispersion of STA on the surface. Surface acidity NH3 -TPD was carried out to determine the surface acidity of 5CuxSTA/Al2 O3 catalysts (see Fig. 2). The 5Cu/Al2 O3 catalyst showed a desorption peak at 410 K, which can be assigned to the surface acidity of Al2 O3 . It was also observed that the acidity of 5Cu/Al2 O3 catalyst could be tuned by the addition of STA, and all the 5Cu-xSTA/Al2 O3 showed a new desorption peak at 560 K, which may be related to the strong acid nature of STA.34 The area of the desorption peak increased signicantly with increasing

Table 1. BET of catalysts Catalysts 0Cu-0STA/Al2 O3 5Cu-0STA/Al2 O3 5Cu-3STA/Al2 O3 5Cu-5STA/Al2 O3 5Cu-15STA/Al2 O3 5Cu-30STA/Al2 O3 BET surface area (m2 g1 ) 293 287 276 262 226 202 Average pore diameter (nm) 10.2 10.3 10.0 9.9 10.5 10.2 Pore volume (cm3 g1 ) 0.75 0.74 0.65 0.62 0.57 0.52

Figure 1. XRD patterns of 5Cu-xSTA/Al2 O3 (a: x=0; b: x=3; c: x=5; d: x=15; e: x=30).

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Table 2. Effect of STA loading on the catalytic performance Selectivity (%) a Catalysts 5Cu-0STA/Al2 O3 5Cu-3STA/Al2 O3 5Cu-5STA/Al2 O3 5Cu-15STA/Al2 O3 5Cu-30STA/Al2 O3 0Cu-5STA/Al2 O3 Conversion (%) 1,2-PD 1-PO EG EtOH MeOH 60.6 77.6 90.1 41.9 8.6 3.7 85.2 87.8 89.7 91.6 92.1 1.0 1.3 1.5 1.2 1.0 8.8 5.8 4.2 1.6 1.0 0.4 0.4 0.5 0.5 0.4 1.8 1.7 2.0 1.5 1.5

Reaction conditions: 10% (w/w) glycerol aqueous solution; H2 pressure: 6 MPa; catalyst weight: 4 g; reaction temperature: 513 K; LHSV: 0.9 h1 . a 1,2-PD = 1,2-propanediol; 1-PO = 1-propanol; EG = ethylene glycol, EtOH=ethanol; MeOH = methanol.

Figure 2. NH3 -TPD proles of 5Cu-xSTA/Al2 O3 (a: x=0; b: x=3; c: x=5; d: x=15; e: x=30).

(w/w), and meanwhile, the intensity of the low temperature peak increased dramatically with increasing STA loading. This clearly demonstrates that the reducibility of Cu species was promoted by the addition of STA due to the weakening of the CuOAl2 O3 interaction. In this case, the one reduction peak around 500 K may be ascribed to the reduction of CuO to metallic Cu.31 It should be noted that all the catalysts are readily reduced before the reaction under the conditions used in this work. Catalytic performance The catalytic performance of the 5Cu-xSTA/Al2 O3 catalysts in glycerol hydrogenolysis is shown in Table 2. It can be observed that the presence of STA improved the conversion of glycerol within a 5% (w/w) loading, beyond which the conversion decreased rapidly. According to the results of NH3 -TPD, more acid sites in the catalysts at high STA content may be responsible for the decrease of glycerol conversion. As the acid sites can result in coking,8,37 catalyst deactivation may result. It is also worth noting that glycerol conversion was as low as 3.7% over 5STA/Al2 O3 (see Table 2) compared with the high conversion over 5Cu-5STA/Al2 O3 , indicating that Cu played a key role in glycerol conversion, which is consistent with previous reports.19,38 It is believed that the catalytic hydrogenolysis of glycerol requires a bi-functional catalyst system, in which glycerol dehydration to dehydrated intermediates occurs and then the hydrogenation takes place simultaneously.3,15,17,19 In the present 5Cu-xSTA/Al2 O3 catalysts, STA and Cu serve as two kinds of active sites responsible for high activity and selectivity. Since the 5Cu-5STA/Al2 O3 catalyst showed a better performance, it was used for further investigation of the effect of reaction conditions on performance. Table 3 gives the inuence of temperature on glycerol conversion and 1,2-PD selectivity. As the temperature was increased from 453 K to 543 K, glycerol conversion increased from 2.5% to 97.4%, and the selectivity of 1,2-PD decreased from 97.3% to 37.7%. However, the selectivity of side products such as ethylene glycol and 1-propanol increased dramatically. So, it can be concluded that the higher temperature results in more side reactions. A proper temperature was then needed for conversion of the dehydrated intermediate to l,2-PD, and at a relatively higher temperature, further hydrogenolysis of l,2-PD into unwanted by-products is favored. Moreover, Cucontaining catalysts show poor CC bond cleavage activity but efcient activity for CO bond hydro-dehydrogenation, which is critical for the hydrogenolysis of glycerol.

Figure 3. TPR proles of 5Cu-xSTA/Al2 O3 (a: x=0; b: x=3; c: x=5; d: x=15; e: x=30).

STA loading, suggesting that more acid sites were formed. The interaction between support and STA had a positive effect on the acidity and improved the proportion of weak and medium acid sites, thus the current increase in acid sites could not be only related to the increasing loading of STA, but also to its interaction with Al2 O3 . Reducibility For supported metal catalysts, the metalsupport interaction can inuence performance. H2 -TPR was carried out to measure the reducibility of the 5Cu-xSTA/Al2 O3 catalysts and the effect of STA on CuOAl2 O3 interaction (see Fig. 3). Two reduction peaks centered at 500 K and 525 K were observed for the 5Cu/Al2 O3 catalyst, which can be attributed to the reduction of Cu2+ to Cu+ and Cu+ to Cu0 , respectively.35,36 The higher temperature needed for the reduction may result from CuOAl2 O3 interaction.36 Upon addition of STA, the intensity of the high temperature peak gradually decreased, and disappeared at a STA loading up to 15%

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Table 3. Effect of temperature on the catalytic performance Selectivity (%)a Reaction temperature (K) Conversion (%) 1,2-PD 1-PO 453 483 513 543 2.5 31.2 90.1 97.4 97.3 95.4 89.7 37.7 1.6 1.5 49.5 EG 4.2 5.4 EtOH MeOH 1.3 0.5 1.8 2.0 2.3

Reaction conditions: 10% (w/w) glycerol aqueous solution; H2 pressure: 6 MPa; catalyst weight: 4 g; LHSV: 0.9 h1 . a 1,2-PD = 1,2-propanediol; 1-PO = 1-propanol; EG = ethylene glycol, EtOH=ethanol; MeOH = methanol.

Table 4. Effect of liquid hourly space velocity on the catalytic performance Selectivity (%)a Space velocity Conversion (%) 1,2-PD 1-PO (h1 ) 1.8 0.9 0.45 81.2 90.1 95.7 95.1 89.7 70.5 1.1 1.5 15.1 EG 4.2 6.8 EtOH MeOH 0.3 0.5 2.8 2.0 2.1

Figure 4. Long-term stability of 5Cu-5STA/Al2 O3 catalyst.

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Reaction conditions: 10% (w/w) glycerol aqueous solution; H2 pressure: 6 MPa; catalyst weight: 4 g; reaction temperature: 513 K. a 1,2-PD = 1,2-propanediol; 1-PO = 1-propanol; EG = ethylene glycol, EtOH=ethanol; MeOH = methanol.

The consecutive conversion of the dehydrated intermediate to other products via l,2-PD was also observed when the reaction was performed under different liquid hourly space velocities (LHSVs), as shown in Table 4. A longer residence time gives rise to lower l,2PD selectivity due to its further conversion and degradation. This demonstrated that the glycerol conversion decreased with the increase of LHSV, and in the present work, however, a reasonable glycerol conversion and l,2-PD selectivity was observed even at LHSV of 1.8 h1 , which was the best result in the open literature.30,31 The long-term test was carried out at 513 K, 6 MPa and LHSV of 0.9 h1 , and as shown in Fig. 4, both glycerol conversion and l,2-PD selectivity were maintained at the initial levels over 250 h with no catalyst deactivation.

CONCLUSIONS
The introduction of STA into Cu/Al2 O3 catalysts led to both high activity and selectivity towards the synthesis of 1,2-PD from the hydrogenolysis of glycerol. Catalyst characterization indicated that the acidity of catalyst can be tuned by the addition of STA, and more acid sites were formed with increasing STA loading. There existed a synergistic effect between Cu and STA species on the catalysts, and the existence of STA changed the reduction behavior of copper oxides. As a result, the activity of glycerol hydrogenolysis depended not only on the acid sites but also the metal sites. The reaction can proceed via a two-step catalyzed pathway, i.e. the acid sites provided by STA/Al2 O3 catalyzed the dehydration of glycerol followed by subsequent hydrogenation to 1,2-PD over metallic Cu.

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