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Catalysis Today 212 (2013) 120– 126

Catalysis Today 212 (2013) 120– 126 Contents lists available at SciVerse ScienceDirect Catalysis Today j ourg author at: State Ke y Laborator y of Coal Conversion, Institute of Coal Chemist r y , C h i n e s e A c a d e m y o f S c i e n c e s , T a i y u a n 0 3 0 0 0 1, PR China. Tel.: +86 351 7117097; fax: +86 351 7560668. E-mail address: zhuyulei@sxicc.ac.cn (Y. Zhu). 0920-5861/$ – see front matter © 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.cattod.2012.09.011 synthesis via hydration of acrolein or hydroformylation of ethyl- ene oxide [12] . The development of an alternative environmentally benign process for the production of 1,3-PDO based on the biomass- derived glycerol as a sustainable feedstock is a real challenge. Supported Ir, Pt, Ru, Rh, Pd and Cu catalysts have been used for glycerol hydrogenolysis to 1,3-PDO [9,10,13–21] . Among these catalysts, supported Pt catalysts are more selective for this reac- tion than others. To obtain 1,3-PDO effectively, it is necessary to add acid component to the catalysts due to the bi-functional mechanism. Previous research [9,22] shows that hydrogenoly- sis of glycerol to 1,3-PDO proceeds via dehydration of glycerol to 3-hydroxypropaldehyde (3-HPA) followed by hydrogenation. According to the above mechanism, acid catalysts play an important role in glycerol hydrogenolysis. Various acid catalysts including H WO , H SO , sulfated zirconia, WO /ZrO , and WO /TiO /SiO have been used [9,10,18,21,23,24] . Studies by Chaminand et al. [23] showed that hydrogenolysis of glycerol to 1,3-PDO on Rh/SiO cat- alyst achieved 4% yield in the presence of H WO at 200 C and 8.0 MPa. Tomishige and co-workers [18] reported that the yield of 1,3-PDO reached 38% over Ir-ReO /SiO catalyst with H SO as an additive in a batch reactor. However, the liquid acids would cause several problems in terms of catalyst separation, reactor corro- sion and environmental protection. Recently, Oh et al. [24] have communicated the use of Pt-sulfated zirconia with 1,3-dimethyl-2- imidazolidinone in glycerol hydrogenolysis but such strong acidic " id="pdf-obj-0-6" src="pdf-obj-0-6.jpg">

Contents lists available at SciVerse ScienceDirect

Catalysis Today

j our nal homep a g e: www.elsevier.com/locate/cattod

Catalysis Today 212 (2013) 120– 126 Contents lists available at SciVerse ScienceDirect Catalysis Today j ourg author at: State Ke y Laborator y of Coal Conversion, Institute of Coal Chemist r y , C h i n e s e A c a d e m y o f S c i e n c e s , T a i y u a n 0 3 0 0 0 1, PR China. Tel.: +86 351 7117097; fax: +86 351 7560668. E-mail address: zhuyulei@sxicc.ac.cn (Y. Zhu). 0920-5861/$ – see front matter © 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.cattod.2012.09.011 synthesis via hydration of acrolein or hydroformylation of ethyl- ene oxide [12] . The development of an alternative environmentally benign process for the production of 1,3-PDO based on the biomass- derived glycerol as a sustainable feedstock is a real challenge. Supported Ir, Pt, Ru, Rh, Pd and Cu catalysts have been used for glycerol hydrogenolysis to 1,3-PDO [9,10,13–21] . Among these catalysts, supported Pt catalysts are more selective for this reac- tion than others. To obtain 1,3-PDO effectively, it is necessary to add acid component to the catalysts due to the bi-functional mechanism. Previous research [9,22] shows that hydrogenoly- sis of glycerol to 1,3-PDO proceeds via dehydration of glycerol to 3-hydroxypropaldehyde (3-HPA) followed by hydrogenation. According to the above mechanism, acid catalysts play an important role in glycerol hydrogenolysis. Various acid catalysts including H WO , H SO , sulfated zirconia, WO /ZrO , and WO /TiO /SiO have been used [9,10,18,21,23,24] . Studies by Chaminand et al. [23] showed that hydrogenolysis of glycerol to 1,3-PDO on Rh/SiO cat- alyst achieved 4% yield in the presence of H WO at 200 C and 8.0 MPa. Tomishige and co-workers [18] reported that the yield of 1,3-PDO reached 38% over Ir-ReO /SiO catalyst with H SO as an additive in a batch reactor. However, the liquid acids would cause several problems in terms of catalyst separation, reactor corro- sion and environmental protection. Recently, Oh et al. [24] have communicated the use of Pt-sulfated zirconia with 1,3-dimethyl-2- imidazolidinone in glycerol hydrogenolysis but such strong acidic " id="pdf-obj-0-18" src="pdf-obj-0-18.jpg">

Hydrogenolysis of glycerol to 1,3-propanediol over bifunctional catalysts containing Pt and heteropolyacids

Shanhui Zhu a,b , Yanan Qiu c , Yulei Zhu a,d, , Shunli Hao d , Hongyan Zheng d , Yongwang Li a,d

a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, PR China b Graduate University of Chinese Academy of Sciences, Beijing 100039, PR China c Institute of Science & Technology Information of Shanxi, Taiyuan 030001, PR China d Synfuels China Co. Ltd., Taiyuan 030032, PR China

a r t i c

l e

i n f o

Article history:

Received 11 March 2012 Received in revised form 27 June 2012

Accepted 2 September 2012

Available online 18 October 2012

Keywords:

Glycerol

Hydrogenolysis

1,3-Propanediol

Heteropolyacids

a b s t r a c t

Hydrogenolysis of glycerol to 1,3-propanediol was conducted over zirconia supported bifunctional cata- lysts containing Pt and heteropolyacids using H 4 SiW 12 O 40 (HSiW), H 3 PW 12 O 40 (HPW) and H 3 PMo 12 O 40 (HPMo) as active compounds. Pt/ZrO 2 was also examined for comparison. The as-prepared catalysts were characterized by BET, CO chemisorption, XRD, Raman spectra, NH 3 -TPD and FTIR of adsorbed pyridine. Compared with Pt/ZrO 2 , heteropolyacids modified Pt/ZrO 2 catalysts showed higher acidity and better

catalytic performance of glycerol hydrogenolysis to 1,3-propanediol. Among them, Pt-HSiW/ZrO 2 exhib- ited superior performance due to the high Brønsted acid sites and good thermal stability. Independent of the heteropolyacid type, the concentration of Brønsted acid sites appeared as a key to the selective formation of 1,3-propanediol from glycerol hydrogenolysis, whereas the concentration of Lewis acid sites was related to the formation of 1,2-propanediol. We also investigated the reaction network and proposed a possible reaction pathway.

© 2012 Elsevier B.V. All rights reserved.

1. Introduction

The catalytic transformation of biomass-derived feedstocks for the synthesis of value-added fuels, chemicals and materials has been attracting much attention, due to the diminishing reserves and rising price of fossil resources [1,2]. Recent development of biodiesel production by transesterification of plant oils and animal fat has made a large amount of glycerol available as a renewable feedstock for the production of various fuels and valuable chemicals [2–5]. Significant research efforts have been focused on the conver- sion of glycerol by various catalytic processes such as reforming, oxidation, dehydration, hydrogenolysis, etherification, esterifica- tion and so on [3–10]. Hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) and 1,3-propanediol (1,3-PDO) is a noticeable pathway due to its production of renewable value-added chemicals. 1,3-PDO owes much higher economical value than 1,2-PDO, in particular, as an important monomer in the synthesis of polyester fibers [4,5,11]. Industrial production of 1,3-PDO is currently based on chemical

Corresponding author at: State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, PR China. Tel.: +86 351 7117097; fax: +86 351 7560668. E-mail address: zhuyulei@sxicc.ac.cn (Y. Zhu).

0920-5861/$ – see front matter © 2012 Elsevier B.V. All rights reserved.

http://dx.doi.org/10.1016/j.cattod.2012.09.011

synthesis via hydration of acrolein or hydroformylation of ethyl- ene oxide [12]. The development of an alternative environmentally benign process for the production of 1,3-PDO based on the biomass- derived glycerol as a sustainable feedstock is a real challenge. Supported Ir, Pt, Ru, Rh, Pd and Cu catalysts have been used for glycerol hydrogenolysis to 1,3-PDO [9,10,13–21]. Among these catalysts, supported Pt catalysts are more selective for this reac- tion than others. To obtain 1,3-PDO effectively, it is necessary to add acid component to the catalysts due to the bi-functional mechanism. Previous research [9,22] shows that hydrogenoly- sis of glycerol to 1,3-PDO proceeds via dehydration of glycerol to 3-hydroxypropaldehyde (3-HPA) followed by hydrogenation. According to the above mechanism, acid catalysts play an important role in glycerol hydrogenolysis. Various acid catalysts including H 2 WO 4 , H 2 SO 4 , sulfated zirconia, WO 3 /ZrO 2 , and WO 3 /TiO 2 /SiO 2 have been used [9,10,18,21,23,24]. Studies by Chaminand et al. [23] showed that hydrogenolysis of glycerol to 1,3-PDO on Rh/SiO 2 cat- alyst achieved 4% yield in the presence of H 2 WO 4 at 200 C and 8.0 MPa. Tomishige and co-workers [18] reported that the yield of 1,3-PDO reached 38% over Ir-ReO x /SiO 2 catalyst with H 2 SO 4 as an additive in a batch reactor. However, the liquid acids would cause several problems in terms of catalyst separation, reactor corro- sion and environmental protection. Recently, Oh et al. [24] have communicated the use of Pt-sulfated zirconia with 1,3-dimethyl-2- imidazolidinone in glycerol hydrogenolysis but such strong acidic

S. Zhu et al. / Catalysis Today 212 (2013) 120– 126

121

catalysts deactivate quickly as carbonaceous deposits block the cat- alyst surface. Additionally, the usage of organic solvent will greatly reduce the environmental and economical viability. Heteropolyacids (HPAs) have demonstrated to display out- standing catalytic performance for both homogeneous and heterogeneous acid-catalyzed reactions because of its well-defined structure and widely tunable acidity [8,25–27]. HPAs possess unique physicochemical properties, with their structural mobil- ity and multifunctionality, which is useful in industrial processes such as the liquid–phase dehydration of alcohols and hydration of esters or olefins [26–28]. Additionally, heterogeneous acid catal- ysis by HPAs has attracted much interest due to its potential of great economic rewards and green benefits. Compared to con- ventional solid acid catalysts such as oxides and zeolites, HPAs possess strong acidity, uniform acid sites and easily tunable acid- ity. Generally, tungsten HPAs owns stronger acidity, higher thermal stability and lower oxidation potential than molybdenum HPAs, which makes tungsten HPAs used more widely [29]. However, HPAs lack thermal stability and leach easily in polar solvents. To solve this problem, HPAs are often immobilized on supports such as SiO 2 or ZrO 2 . Kozhevnikov and co-workers [27] have studied the interaction between HPW and support with ammonia adsorption calorimetry, MAS NMR and FTIR and suggested increasing interac- tion in the following order: SiO 2 < TiO 2 < Nb 2 O 5 < ZrO 2 . Moreover, our previous study [13] showed that the Pt-HSiW/ZrO 2 catalyst was rather durable during one-step hydrogenolysis of glycerol to biopropanols. Taken together, it is worthwhile to study supported HPAs as acid catalysts for glycerol hydrogenolysis. In the present investigation, several zirconia supported Pt- HPAs (HSiW, HPW and HPMo) bi-functional catalysts were prepared, characterized, and tested in aqueous solution for glyc- erol hydrogenolysis. Special emphasis was also laid on formation route of glycerol hydrogenolysis and degradation based on the catalytic performance in the reaction of products and detected intermediates.

2. Experimental

  • 2.1. Catalyst preparation

ZrO 2 (Jiangsu Qianye Co., Ltd., China) was used as support of the catalysts. H 2 PtCl 6 ·6H 2 O (AR), HSiW (AR), HPW (AR) and HPMo (AR) were purchased from Sinopharm Chemical Reagent Co., Ltd. All the catalysts were prepared by incipient wetness impregnation method. Typical procedures for the preparation of Pt-HSiW/ZrO 2 catalyst are as follows. The Pt/ZrO 2 catalyst was prepared by impregnation of zirconia support with an aqueous solution of H 2 PtCl 6 ·6H 2 O. The impregnated sample was dried overnight at 110 C and then calcined at 400 C in static air for 4 h. After impreg- nated HSiW onto Pt/ZrO 2 , Pt-HSiW/ZrO 2 was dried overnight at 110 C and then calcined at 350 C in static air for 4 h. Pt-HPW/ZrO 2 and Pt-HPMo/ZrO 2 were prepared in the similar way to that of Pt-HSiW/ZrO 2 . The Pt and HPAs loadings were fixed at 2 wt.% and 15 wt.%, respectively.

  • 2.2. Catalyst characterization

N 2 adsorption–desorption isotherms were recorded at 196 C using a Micromeritics ASAP 2420 instrument after degassing at 300 C for 8 h in vacuum. BET surface area and BJH pore size distribution were calculated by desorption isotherms. CO chemisorption was measured at 50 C in Auto Chem. 2920 equipment (Mircromeritics, USA). Prior to the measurement, about 0.2 g catalyst sample was first reduced in situ for 2 h in pure H 2 at

200 C, then purged with He at the same temperature for 1 h and finally cooled down to 50 C. The CO chemisorption was operated by pulse injection of pure CO at 50 C. The Pt particle size was cal- culated by assuming an adsorption of one CO molecule per surface platinum atom. Powder X-ray diffraction (XRD) patterns were conducted at room temperature on a D2/max-RA X-ray diffractometer (Bruker, Germany) using Cu K radiation at 30 kV and 10 mA. The X-ray patterns were recorded in 2 values ranging from 10 to 90 at the scanning rate of 5 /min. Raman spectra were recorded with a LabRAM HR800 System equipped with a CCD detector at room temperature. The 325 nm of the He-Cd laser was used as the exciting source with a power of 30 MW. NH 3 -TPD was carried out in the same apparatus as CO chemisorption. Prior to each run, the catalyst sample (0.3 g) was pretreated in He at 350 C for 1 h, then cooled to 100 C and was saturated with pure NH 3 for 30 min. After being purged with He for 30 min, the sample was heated to 700 C at a heating rate of 10 C/min and the NH 3 desorption was monitored with a TCD detector. To evaluate and analyze the nature and acid amount of cata- lysts, FTIR spectra of adsorbed pyridine (Py-IR) of solid samples were carried out on a VERTEX70 (Bruker) FT-IR spectrophotome- ter, equipped with a deuterium triglycine sulphate (DTGS) detector. Prior to pyridine adsorption, the samples were heated to 300 C under vacuum, and then cooled to 30 C. The Py-IR spectra were then recorded at 200 C after applying vacuum for 30 min. The quantitative calculation of Brønsted and Lewis acid sites was deter- mined by the integrated area of the adsorption bands at about 1540 and 1450 cm 1 , respectively. The acidity of Brønsted and Lewis acid sites was calculated by using the adsorption coefficient values reported in the previous paper [30].

  • 2.3. Catalytic tests

Hydrogenolysis of glycerol was conducted in a vertical fixed- bed reactor (i.d. 12 mm, length 600 mm) with an ice-water trap. In a typical run, 2.0 g catalyst (20–40 mesh) was charged in the con- stant temperature section of the reactor, with quartz sand packed in both ends. Prior to the test, the catalyst sample was in situ reduced in a stream of pure H 2 (100 ml/min) at 200 C for 2 h. After reduction, the system was cooled to the desired temperature. A 10 wt.% glycerol aqueous solution was fed continuously into the reactor with an HPLC pump along with a co-feed H 2 of gas flow- ing at 100 cm 3 min 1 . The liquid and gas products were cooled and collected in a gas–liquid separator immersed in an ice-water trap. The products were obtained when the reaction reached the steady state. Additionally, the reaction performance of 1,3-PDO, 1,2-PDO and ethylene glycol (EG) was also evaluated in order to reveal the reaction pathway of glycerol hydrogenolysis. The liquid products were analyzed by gas chromatography using a capillary column (DB-WAX, 30 m × 0.32 mm) equipped with a FID detector. The tail gas was off-line analyzed by a gas chromatogra- phy with a capillary column (OV-101, 60 m × 0.25 mm) and a TCD detector. The products obtained were also identified by GC–MS. The conversion of glycerol and selectivity of products were calculated as follows:

Conversion (%) moles of glycerol (in) moles of glycerol (out) =

 

moles of glycerol (in)

Selectivity (%) =

moles of one product

× 100.

moles of all products

× 100

122

S. Zhu et al. / Catalysis Today 212 (2013) 120– 126

Table 1 Physicochemical properties and acidities of Pt/ZrO 2 and Pt-HPAs/ZrO 2 catalysts.

Catalyst

Surface area

Pore size

Pore volume

Pt size (nm)

Pt dispersion

Total acidity

Brønsted acidity

Lewis acidity

Total acidity

(m 2 /g 1 )

(nm)

(cm 3 g 1 )

(%)

(mmol NH 3 /g cat ) a ( mol/g cat. ) b

( mol/g cat ) b

( mol/g cat ) b

Pt/ZrO 2

61.0

9.7

0.202

3.01

37.6

0.49

0

164.82

164.82

Pt-HSiW/ZrO 2

54.8

9.8

0.164

3.16

35.8

0.53

86.56

85.59

172.15

Pt-HPW/ZrO 2

57.0

9.4

0.171

3.06

37.0

0.63

62.89

117.18

180.07

Pt-HPMo/ZrO 2

55.3

8.9

0.170

3.69

30.4

0.66

20.09

179.03

199.12

a The amount of acid sites was determined by quantifying the desorbed NH 3 from NH 3 -TPD. b The amount of acid sites was determined by quantifying the desorbed pyridine from Py-IR.

  • 3. Results and discussion

    • 3.1. Catalyst characterizations

      • 3.1.1. Physicochemical properties of catalysts

Table 1 lists the textural properties derived from nitrogen

physisorption isotherms and dispersion of Pt determined by CO

chemisorption of as-prepared catalysts. As can be seen, both surface

area and pore volume of Pt-HPAs/ZrO 2 samples decreased as com-

pared to Pt/ZrO 2 . This decrease may be attributed to pore blockage

caused by heteropolyacids (HPAs) as their Keggin units (diameter

1.2 nm) are small enough to enter mircropores of ZrO 2 [31]. As

shown in Table 1, all the catalysts have small Pt particle size and

good dispersion of Pt. Compared with Pt/ZrO 2 sample, no remark-

able changes of Pt particle size are observed for any supported HPAs

catalysts, implying that the HPAs have little effect on the disper-

sion of Pt. The slight decrease in Pt dispersion of Pt-HPMo/ZrO 2

can be probably related to the partial coverage by HPMo or decom-

position component. Cui et al. [32] have studied the effect of Mo

promoter in iron-based catalysts by high-resolution transmission

electron microscopy and suggested that the presence of high Mo-

Pt-PMo/ZrO 2 Pt-HPW/ZrO 2 Pt-HSiW/ZrO 2 Pt/ZrO 2 ZrO 2 10 20 30 40 50 60
Pt-PMo/ZrO 2
Pt-HPW/ZrO 2
Pt-HSiW/ZrO 2
Pt/ZrO 2
ZrO 2
10
20
30
40
50
60
Intensity

2θ (º)

Fig. 1. XRD patterns of bulk ZrO 2 , Pt/ZrO 2 and Pt-HPAs/ZrO 2 catalysts.

content would weaken the dispersion of iron active sites due to the

below 700 cm 1 interfere with the characteristic Raman bands

coverage effect.

of HPAs species, while the range above 700 cm 1 is free from

Assuming that a cross section of the heteropolyacid (HPA)

characteristic bands of ZrO 2 and hence relevant to the structure

molecule is 144 A ˚ 2 ,

the 15% HPA loading will correspond to

determination of HPAs species. The typical Raman spectra bands of

45 m 2 /g monolayer coverage [27]. Due to the 61.0 m 2 /g surface

Pt-HSiW/ZrO 2 appeared at 998 and 975 cm 1 , which were assigned

area of Pt/ZrO 2 , the supported HPA catalysts can be adequately

viewed as having sub-monolayer HPA coverage. The XRD patterns

(discussed below) confirmed the high dispersion of HPA on the sup-

port surface. The sub-monolayer HPA coverage can ensure strong

HPA/support interaction which can strengthen the thermal stabil-

ity and avoid the leaching of HPA during the reaction. Additionally,

the 15 wt.% loading is sufficient to provide efficient acid catalysis for

glycerol hydrogenolysis. Chai et al. [33] have investigated glycerol

dehydration over a series of HPW loading on zirconia and found

that the 15 wt.% HPW/ZrO 2 showed superior catalytic performance

and most of the Keggin HPW remained intact after calcination up

to 650 C.

The XRD patterns of bulk ZrO 2 and as-prepared catalysts are

illustrated in Fig. 1. ZrO 2 presented in all the samples exhibited

characteristic peaks corresponding to monoclinic phase of ZrO 2

(e.g., 24.1 , 28.3 , 31.5 , 34.3 , 49.4 ) [25]. It is of interest to note

that neither diffraction peaks of Keggin structure nor decomposi-

tion products WO 3 or MoO 3 were detected, most probably because

of the fine dispersion of HPAs or their decomposition species on

the support surface. As discussed above, the sub-monolayer HPA

coverage can avoid HPA crystallites on the support surface. On the

other hand, there were also no diffraction peaks of Pt, indicating

that Pt was highly dispersed on the support surface, which was

well in accordance with the CO chemisorption results.

Raman spectroscopy is known to be well suited for observa-

tion the state of HPAs in the catalysts. As shown in Fig. 2, it has

been identified and attributed Raman bands at 222, 310, 337,

382, 474, 499, 540, 559, 620 and 636 cm 1 to monoclinic zirco-

nia [25], as evidenced by XRD results. The strong Raman bands

to W O symmetric and asymmetric stretching vibrations of HSiW

Keggin structure, respectively [13]. The Pt-HPW/ZrO 2 sample also

displayed two overlapping bands at around 1008 and 990 cm 1 ,

which can be ascribed to the symmetric and asymmetric stretch-

ing vibrations of the terminal W O bond of HPW Keggin anions,

respectively [33]. For Pt-HPMo/ZrO 2 , Raman band for the Keggin

structure was observed at 996 cm 1 but a weak band characteris-

tic of MoO 3 was also identified at 818 cm 1 [31]. Furthermore, a

HPMo 1/4 Pt-HPMo/ZrO 2 HPW 1/4 Pt-HPW/ZrO 2 HSiW 1/4 Pt-HSiW/ZrO 2 ZrO 2 200 400
HPMo
1/4
Pt-HPMo/ZrO 2
HPW
1/4
Pt-HPW/ZrO
2
HSiW
1/4
Pt-HSiW/ZrO
2
ZrO 2
200
400
600
800
1000
1200
Intensity

Raman shift (cm -1 )

Fig. 2. Raman spectra of bulk heteropolyacids and different catalysts.

S. Zhu et al. / Catalysis Today 212 (2013) 120– 126

123

broad band in the range of 980–750 cm 1 was detected, which was

assigned to the stretching vibrations of the bridges between tri-

molybdic groups of Keggin structure caused by dehydration process

[31]. The broadening of this region and presence of MoO 3 indi-

cated a partial decomposition of HPMo Keggin structure during the

high temperature calcination. These observations are consistent

with earlier literature that HPMo would undergo decomposition

at around 350 C to form molybdenum and phosphorous oxides

[29,31].

In comparison with the bulk HPAs, a decrease in the intensity

and a broadening of the Keggin bands over supported HPAs is also

observed. This is probably due to the strong HPAs interaction with

Zr OH groups which is an acid-base reaction where the Zr OH

groups act as a base and HPAs as a Brønsted acid. Some NMR could

also support these findings. Oliveira et al. [25] reported in their

studies on ZrO 2 supported HPW catalyst two lines present at 15.0

and 13.0 ppm. The first chemical shift is related to the Keggin unit

and the second is assigned to zirconia surface bridges. A similar

shift was also observed by Alsalme et al. [27] that indicated strong

interaction between finely dispersed amorphous HPW species and

ZrO 2 .

In summary, it can be concluded that the thermal stability of

HSiW and HPW was stronger than HPMo; the Keggin structure of

HSiW and HPW was well preserved on the support surface, but that

of HPMo was partially destroyed.

  • 3.1.2. Acidic properties of catalysts

Appropriate acidity is essential for the selective hydrogenol-

ysis of glycerol to 1,3-PDO due to the bi-functional mechanism

[9,14,22,34]. The NH 3 -TPD technique has been extensively

employed to probe the acidity of solid acid catalysts. Meanwhile,

the FT-IR after pyridine adsorption is a useful tool to determine the

nature and amount of acid sites.

The NH 3 -TPD profiles of the as-prepared samples are pre-

sented in Fig. 3. Generally the strength of solid acid sites

with TPD profiles can be classified into three types by the

temperature of desorption NH 3 weak (150–300 C), moderate

(300–450 C) and strong (450–650 C) [35]. The NH 3 -TPD result

of Pt/ZrO 2 showed poorly resolved desorption peaks in two dis-

tinct temperature regions, centering about 255 C and 437 C,

respectively. On the other hand, Pt-HPMo/ZrO 2 exhibited an over-

lapping peak including one main peak and two shoulders. In

the case of Pt-HPW/ZrO 2 , two main peaks and a weak shoulder

were observed, around 222 C, 479 C and 157 C, respectively.

Pt-HPMo/ZrO 2 Pt-HPW/ZrO 2 Pt-HSiW/ZrO 2 Pt/ZrO 2 100 200 300 400 500 600 Intensity
Pt-HPMo/ZrO 2
Pt-HPW/ZrO 2
Pt-HSiW/ZrO 2
Pt/ZrO 2
100
200
300
400
500
600
Intensity

Temperature ( o C)

Fig. 3. NH 3 -TPD profiles of Pt/ZrO 2 and Pt-HPAs/ZrO 2 catalysts.

L B Pt-HPMo/ZrO 2 Pt-HPW/ZrO 2 Pt-HSiW/ZrO 2 Pt/ZrO 2 1400 1450 1500 1550 1600 1650
L
B
Pt-HPMo/ZrO 2
Pt-HPW/ZrO 2
Pt-HSiW/ZrO 2
Pt/ZrO 2
1400
1450
1500
1550
1600
1650
1700
Absorbance

Wavenumber (cm -1 )

Fig. 4. Py-IR spectra of Pt/ZrO 2 and Pt-HPAs/ZrO 2 catalysts.

Similar patterns were also obtained for Pt-HSiW/ZrO 2 . The max-

imum TPD peak position of supported HPAs catalysts decreased

in the following order: Pt-HPW/ZrO 2 (479 C) > Pt-HSiW/ZrO 2

(400 C) > Pt-HPMo/ZrO 2 (337 C). The results indicates that the acid

strength of HPAs is in the order of HPW > HSiW > HPMo, consistent

well with the previous report [36]. The amount of acid sites can be

calculated from TPD desorption peak area and the results are listed

in Table 1. The total acidities of the as-prepared catalysts were in an

order of Pt-HPMo/ZrO 2 > Pt-HPW/ZrO 2 > Pt-HSiW/ZrO 2 > Pt/ZrO 2 .

Fig. 4 illustrates the FTIR spectra after pyridine adsorption on

Pt/ZrO 2 and Pt-HPAs/ZrO 2 . Pyridine adsorption at Brønsted acid

sites and Lewis acid sites exhibited typical bands centering at

1540–1548 cm 1 and 1445–1460 cm 1 , respectively [13]. The con-

centration of Brønsted acid and Lewis acid are obtained from the

integral intensities of the typical bands and the results are pre-

sented in Table 1. The results show that Pt/ZrO 2 possessed only

Lewis acid sites. The loading of HPAs resulted in a noticeable

increase in the Brønsted acid on all the samples except that on

HPMo, in which HPMo partially decomposed to MoO 3 . On the

other hand, the amount of Lewis acid sites diminished after HPAs

impregnation except HPMo. The decrease can be related to block-

age of Lewis acid sites due to deposition of HPAs. The increase in

Lewis acid sites of Pt-HPMo/ZrO 2 sample may be derived from the

decomposition product MoO 3 . It can be seen that the total acidity

determined by Py-IR correlated well with the NH 3 -TPD results and

HPAs had significant influence on the relative amount of Brønsted

acid and Lewis acid.

  • 3.2. Effect of supported heteropolyacids on glycerol

hydrogenolysis

The hydrogenolysis of glycerol in aqueous solution was car-

ried out over Pt/ZrO 2 and Pt-HPAs/ZrO 2 . Fig. 5 illustrates glycerol

conversion and 1,3-PDO selectivity as a function of reaction

temperature. Generally glycerol conversion increased remarkably

whereas 1,3-PDO selectivity decreased with the rising temperature

from 160 to 240 C over all catalysts. It can be seen that temperature

has a positive effect on glycerol conversion, as claimed by previous

literature [9,10,13]. However, higher temperature disfavored the

formation of 1,3-PDO and increased by-products 1,2-PDO and 1-

propanol (1-PO). Gong et al. [9] reported similar phenomenon over

bi-functional Pt/WO 3 /TiO 2 /SiO 2 catalyst during hydrogenolysis of

glycerol in a batch reactor and supposed that elevated temperature

can be favorable to activate terminal hydroxyl groups of glycerol.

124

S. Zhu et al. / Catalysis Today 212 (2013) 120– 126

100 Pt/ZrO 2 Pt-HSiW/ZrO 2 80 Pt-HPW/ZrO 2 Pt-HPMo/ZrO 2 60 40 20 0 160 180
100
Pt/ZrO 2
Pt-HSiW/ZrO 2
80
Pt-HPW/ZrO 2
Pt-HPMo/ZrO 2
60
40
20
0
160
180
200
220
240
Conversion (% )

Temperature ( o C )

50 Pt/ZrO 2 Pt-HSiW/Zr O 2 Pt-HPW/ZrO 2 40 Pt-HPMo/ZrO 2 30 20 10 0 160
50
Pt/ZrO 2
Pt-HSiW/Zr O 2
Pt-HPW/ZrO 2
40
Pt-HPMo/ZrO 2
30
20
10
0
160
180
200
220
240
Selectivity of 1,3-PDO (%)

Temperature ( o C )

Fig. 5. Effect of reaction temperature on glycerol conversion and 1,3-PDO selec- tivity over Pt/ZrO 2 and Pt-HPAs/ZrO 2 catalysts. Reaction conditions: 5.0 MPa, 2.0 g catalysts; 10 wt.% glycerol aqueous solution, H 2 /glycerol = 137:1 (molar ratio), WHSV = 0.09 h 1 .

On the other hand, the increase of reaction temperature promoted

the excessive hydrogenolysis of propanediols (PDOs) to propanols

(1-PO + 2-PO).

The activity and main products selectivity of Pt/ZrO 2 and Pt-

HPAs/ZrO 2 in glycerol hydrogenolysis at 180 C are summarized

in Table 2. The Pt/ZrO 2 catalyst produced lower glycerol conver-

sion, a high 1,2-PDO selectivity and very poor 1,3-PDO selectivity,

suggesting that Pt/ZrO 2 was not effective for 1,3-PDO formation.

Lewis acid sites/[µmol/m 2 ]

90 120 150 180 20 20 15 15 10 10 5 5 0 0 0 20
90
120
150
180
20
20
15
15
10
10
5
5
0
0
0
20
40
60
80
1,2-PDO yield/%
1,3-PDO yield/%

Brønsted acid sites/[µmol/m 2 ]

Fig. 6. Correlation between the amount of acids sites and product yield obtained at

180 C of the reaction.

In comparison to Pt/ZrO 2 , supported HPAs catalysts enhanced the

catalytic activity considerably and the most prominent benefit

rose from the significant impact on product distribution. For sup-

ported HPAs catalysts, large amounts of sequential hydrogenolysis

products (1-PO/2-PO) were formed and the selectivity to degrada-

tion products (EG and ethanol) diminished moderately. Among the

four catalysts, Pt-HSiW/ZrO 2 was the most selective catalyst as it

showed 48.1% selectivity to 1,3-PDO at 180 C.

It is well known that the dispersion of active metal and acidity of

catalyst play a key role in the bi-functional hydrogenolysis mech-

anism of glycerol [13,14]. It was found that the addition of HPAs

to Pt/ZrO 2 slightly decreased the surface area and the dispersion of

Pt. These results inferred that the increased hydrogenolysis ability

of Pt-HPAs/ZrO 2 was related to the acidity of catalyst. As shown

in Tables 1 and 2, it can be observed that the conversion increased

gradually with the total amount of acid sites over these catalysts. In

lower reaction temperature, Pt-HPMo/ZrO 2 exhibited the highest

activity related to high amount of acid sites. However, the catalytic

activity became less than other catalysts at 220 and 240 C, prob-

ably due to the bad hydrothermal stability of HPMo. Varisli et al.

[37] reported that HPMo was less stable than HSiW and HPW at

temperatures higher than 200 C in dehydration of ethanol.

It is clearly stated in literature that Brønsted acid sites favors

the removal of the secondary hydroxyl group from glycerol to gen-

erate 1,3-PDO [9,13,24]. As presented in Tables 1 and 2, the yield

to 1,3-PDO is proportional to the concentration of Brønsted acid

sites. A close correlation between the 1,3-PDO yield at 180 C and

the concentration of Brønsted acid sites can be derived, as dis-

played in Fig. 6. Although Brønsted acid sites were not available in

the fresh Pt/ZrO 2 , they could be generated by interaction of Lewis

Table 2 Catalytic performance of glycerol hydrogenolysis over Pt/ZrO 2 and Pt-HPAs/ZrO 2 catalysts at 180 C.

Catalyst

Conversion (%)

Selectivity (%) a

 

1,3-PDO

1,2-PDO

1-PO

2-PO

EG

Ethanol

Acetone

Propanal

Others b

Pt/ZrO 2

18.7

3.9

76.1

3.2

0.6

6.6

3.9

1.2

0.5

4.0

Pt-HSiW/ZrO 2

24.1

48.1

16.5

21.8

4.5

0.7

0.9

0.2

1.1

6.2

Pt-HPW/ZrO 2

25.5

32.9

10.9

37.9

5.2

0.6

4.2

0.7

5.3

2.3

Pt-HPMo/ZrO 2

27.1

7.8

39.2

30.4

3.2

1.0

1.9

1.1

1.4

14.0

Reaction conditions: 180 C, 5.0 MPa, 2.0 g catalysts; 10 wt.% glycerol aqueous solution, H 2 /glycerol = 137:1 (molar ratio), WHSV = 0.09 h 1 . a 1,3-PDO, 1,3-propanediol; 1,2-PDO, 1,2-propanediol; 1-PO, 1-propanol; 2-PO, 2-propanol; EG, ethylene glycol. b Others: acetol, methanol, acetic acid, propionic acid, propane, methane, and so on.

S. Zhu et al. / Catalysis Today 212 (2013) 120– 126

Table 3 Reaction results of various reactants over Pt-HSiW/ZrO 2 .

125

Reactant

Conversion (%)

Selectivity (%) a

1,3-PDO

1,2-PDO

1-PO

2-PO

EG

Ethanol

Acetone

Propanal

Others b

Glycerol

1,2-PDO

1,3-PDO

EG

24.1

47.1

9.1

53.7

48.1

0.0

0.0

16.5

0.0

0.0

21.8

85.2

96.5

0.0

4.5

8.9

1.0

0.0

0.7

0.0

0.0

0.9

1.8

1.5

97.7

0.2

2.0

0.0

0.0

1.1

0.7

0.6

0.0

6.2

1.4

0.4

2.3

Reaction conditions: 180 C, 5.0 MPa, 2.0 g catalysts; 10 wt.% aqueous solution of reactant, WHSV = 0.09 h 1 . a 1,3-PDO, 1,3-propanediol; 1,2-PDO, 1,2-propanediol; 1-PO, 1-propanol; 2-PO, 2-propanol; EG, ethylene glycol. b Others: acetol, methanol, acetic acid, propionic acid, propane, methane, and so on.

acid sites with steam to give rise to 1,3-PDO. Among the tested

supported HPAs catalysts, HSiW led to the highest 1,3-PDO yield

whereas HPMo displayed the lowest 1,3-PDO yield. The excellent

performance of HSiW was attributed to high Brønsted acid sites and

hydrolytic stability even in hydrothermal environment. Atia et al.

[31] reported that supported HSiW was more selective than HPW

and HPMo in glycerol dehydration to acrolein which has the same

intermediate 3-HPA as 1,3-PDO. Tsukuda et al. [36] also acclaimed

that HSiW showed high performance in glycerol dehydration due

routes. The reaction results are summarized in Table 3. Regarding

the reaction activity, 1,3-PDO was much lower than 1,2-PDO and

glycerol. Additionally, the selectivity to 1-PO was much higher than

that to 2-PO in the hydrogenolysis of 1,3-PDO or 1,2-PDO, which

was related to the high selectivity of 1-PO formation in the glycerol

hydrogenolysis. The 1-PO/2-PO ratio in the glycerol hydrogenolysis

was similar to that in the 1,2-PDO hydrogenolysis. The combined

results indicate that 1-PO and 2-PO are mainly formed via 1,2-PDO

in the glycerol hydrogenolysis, consistent well with the previous

to high Brønsted acid strength and resistance to water. On the other

hand, HPMo always showed the lowest 1,3-PDO selectivity whereas

high 1,2-PDO selectivity due to partial decomposition of HPMo,

high Lewis acid sites and bad thermal stability.

According to the literature [8,38], Lewis acid sites are respon-

sible for the glycerol dehydration to acetol which can further

hydrogenation to form 1,2-PDO over metal catalysts. Therefore, we

attempted to correlate the concentration of Lewis acid sites with

1,2-PDO yield at 180 C. Unfortunately, the correlation is not good,

which could be mainly attributed to sequential hydrogenolysis of

1,2-PDO to propanols. Qin et al. [10] proposed that propanols are

mainly formed via 1,2-PDO in glycerol hydrogenolysis, and it was

also verified by our separate experiment, as discussed later. Thus,

the calculated 1,2-PDO yield should include the observed 1,2-PDO

and the part converted to propanols. It is interesting to find that

a close correlation between the calculated 1,2-PDO yield at 180 C

and the concentration of Lewis acid sites was obtained, as illus-

trated in Fig. 6.

  • 3.3. Reaction mechanism of glycerol hydrogenolysis over

Pt-HSiW/ZrO 2

report [10].

A plausible reaction pathway for glycerol hydrogenolysis and

degradation is presented in Fig. 7. Reaction routes of hydrogenoly-

sis products will be discussed firstly. Previous research [22] shows

that PDOs formation proceeds via dehydration of glycerol to ace-

tol and 3-HPA on acid catalyst and consecutive hydrogenation to

1,2-PDO and 1,3-PDO over metal catalysts, respectively. Alhanash

et al. [8] have suggested that acetol was formed on Lewis acid

sites whereas acrolein on Brønsted acid sites in glycerol dehydra-

tion, which is well in agreement with our results. In the case of

Pt/ZrO 2 (Table 2), the main product was 1,2-PDO due to its large

Lewis acid sites. However, addition of HSiW to Pt/ZrO 2 catalysts

improved the catalytic activity and 1,3-PDO selectivity remarkably

because of the enhanced Brønsted acid. To corroborate this point

further, we also investigated the Pt-free HSiW/ZrO 2 catalyst for

glycerol hydrogenolysis under identical conditions as Pt/ZrO 2 at

180 C. The result showed that glycerol conversion was only 2.3%

and the primary product was acrolein with a selectivity of 66.5%,

whereas the selectivity of acetol was only 13.3%, consistent well

with the conclusion reported by Alhanash et al. [8]. The 3-HPA

was not detected in any experiment whereas acetol was observed,

implying that acetol is much less reactive than 3-HPA. 3-HPA can

Activity tests of reaction products 1,2-PDO, 1,3-PDO and

dehydrate into acrolein or hydrogenate to 1,3-PDO. Additionally,

EG over Pt-HSiW/ZrO 2 were also examined under similar

3-HPA can further decompose to form acetaldehyde and formalde-

conditions

as used for glycerol to elucidate the reaction hyde through a retro-aldol condensation reaction. Then acetic
as
used
for
glycerol
to
elucidate
the
reaction
hyde through a retro-aldol condensation reaction. Then acetic
OH + CH 4
O
O
OH
-H 2 O
+H 2
+H
2
OH
OH
OH
-H 2 O
-H 2 O
+H 2
OH
O
-H 2 O
[O]
-H 2 O
HO
OH
+H 2
HO
O
HO
OH
OH
OH
O
O
-H 2
[O]
-H 2
O
+
O
OH
-CO
HO
OH
HO
O
HO
-H 2 O
+H 2
OH
OH
O
OH
O

Fig. 7. Reaction scheme of glycerol hydrogenolysis and degradation reactions.

126

S. Zhu et al. / Catalysis Today 212 (2013) 120– 126

acid can be formed by the oxidation of acetaldehyde in aqueous

solution.

Propanal and acetone are formed through PDOs dehydra-

tion and then hydrogenate to 1-PO and 2-PO, respectively. It is

reported that propanal can be further oxidized to produce pro-

pionic acid in aqueous solution [39]. Ethanol and methane are

produced by C C cleavage of 1,2-PDO. Additionally, trace propane

is formed by sequential hydrogenolysis of propanols. Methane

can be formed from methanol hydrogenation or from PDOs

degradation.

Degradation product EG showed higher hydrogenolysis activity

than glycerol and PDOs over Pt-HSiW/ZrO 2 . The fact that EG was

not formed in the reaction of PDOs hydrogenolysis indicated

that it was formed directly from glycerol. The EG formation

proceeds via dehydrogenation of glycerol to glyceraldehyde and

subsequent C C bond cleavage. The mechanism by which the

C C bond cleavage occurs on Pt sites is subject to some debate

that it proceeds via decarbonylation or retro-aldol condensation.

In the presence of base, Maris and Davis [40] have asserted that

EG formation is attributed to retro-aldol reaction rather than

through decarbonylation. King et al. [7] proposed that C C bond

cleavage was formed through glyceraldehyde decarbonylation

under an acidic condition. It seems that both offer plausible

pathways which are highly dependent on the operation conditions

and catalytic system used. Very recently, Vlachos and co-works

[41] have identified the most favorable decomposition pathway

of glycerol on Pt with quantum mechanics calculations and the

pathway is shown as follows: C 3 H 8 O 3 CHOHCHOHCH 2 OH

CHOHCHOHCHOH CHOHCOHCHOH COHCOHCHOH

COCOHCHOH CO + COHCHOH. These above results indicate

that EG formation in our reaction chemistry proceeded most

probably via decarbonylation of glyceraldehyde. However, not CO

but CO 2 was detected in glycerol hydrogenolysis. Wawrzetz et al.

[42] have observed similar phenomenon during aqueous-phase

hydrogenolysis of glycerol over Pt/Al 2 O 3 and argued that CO 2

is generated by decarbonylation of glyceraldehyde followed by

water gas shift. Additionally, glyceraldehyde is also not detected

because it is very reactive. Interestingly, we observed dihydroxy-

acetone which can be produced from glycerol dehydrogenation or

glyceraldehyde transformation. Liang et al. [6] have disclosed that

glyceraldehyde is more reactive than dihydroxyacetone over Pt

based catalyst. Glyceraldehyde was not detected in our products

most likely because it can undergo decarbonylation or convert to

dihydroxyacetone rapidly. As shown in Table 3, the major product

of EG hydrogenolysis was ethanol and trace of acetaldehyde.

The EG can undergo dehydration to acetaldehyde intermediate

followed by subsequent hydrogenation to ethanol.

4. Conclusions

The results of this study indicate that heteropolyacids mod-

ified Pt/ZrO 2 catalysts were effective in glycerol hydrogenolysis

to 1,3-PDO. Addition of HPAs to Pt/ZrO 2 catalysts increased the

catalytic activity and 1,3-PDO selectivity considerably due to the

enhanced acidity. Compared to Pt-HPW/ZrO 2 and Pt-HPMo/ZrO 2 ,

Pt-HSiW/ZrO 2 obtained the highest selectivity to 1,3-PDO, which

was probably related to the high Brønsted acid sites and good

thermal stability. The 1,3-PDO yield was proportional to the con-

centration of the Brønsted acid sites, whereas the 1,2-PDO yield

was proportional to the concentration of Lewis acid sites. Finally,

the reaction pathways have been proposed, and the results indi-

cate that 1-PO and 2-PO are mainly formed via 1,2-PDO in glycerol

hydrogenolysis. In addition, the formation of by-product EG is con-

firmed to originate from decarbonylation of glyceraldehyde under

given experimental conditions.

Acknowledgements

This work was financially supported by the Natural Science

Foundation of China (No. 20976185), and the Major State Basic

Research Development Program of China (973 Program) (No.

2012CB215305).

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