Transcript Pd – Bi nanoparticles on anionic

Joint Slovak-Hungarian Laboratory for Development of
Catalyzed Chemical Processes of Biomass Utilization
Pd-Bi nanoparticles on anionic-exchange
resins for oxidation of polyols
Ing. Stanislav Vajíček
Doc. Ing. Magdaléna Štolcová PhD.
Oxidation of glycerol
N. Dimitratos, J. A. Lopez, D. Lennon, F. Porta, L. Prati, A. Villa, Cat. Letters, 108 (2006) 147-154
Oxidation products - utilization
Glyceric acid1
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coolant in the form of quaternary ammonium salts
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preparation of surfactants
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production of synthetic analogues of phospholipids
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preparation of polymers
Dihydroxyacetone1
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production of self-tanning agents
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treatment of sen wine quality
Glycolic Acid2
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water softening, solvent
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cosmetics - products for hair and skin
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textile and leather industries – coloring
Tartronic acid2
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trap of dissolved oxygen in alkaline water
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protection of metal surfaces against corrosion
β-hydroxypyruvic acid3
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preparation of L-serine - production of biologically active peptides
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cosmetics - creams, face masks

essential amino acids
1H.
Habe, T. Fukuoka, D. Kitamoto, K. Sakaki, Applied Microbiological Biotechnology, 84 (2009) 445-452.
2P.
M. Bizot, B. R. Bailey, P. D. Hicks, US Patent No.: 5,750,037 (1998)
3A.
Abbadi, H. van Bekkum, Applied Catalysis A: General, 148 (1996) 113-122.
Oxidation of primary alcohol groups of
glycerol
• alkali region – oxidation of primary alcohol groups
• mono- and dicarboxylic acids
• catalysts based on Pd, Pd-Bi, Au, Au-Pd, Pt
• support: active carbon, graphit, metal oxides* (TiO2, CeO2, Al2O3, SiO2)
• metal particle size
* I. Sobczak, K. Jagodzinska, M. Ziolek, Catal. Today, 158, (2010), 121-129
Garcia (1995)
•
cat. 5 wt.% Pd/C – impregnation of charcoal with PdCl42-
•
pH = 11, 60°C
•
max. yield of GLYA 60% at 90% conversion of GLY
Bianchi (2005)
•
cat. 1 wt.% Pd/C
•
impregnation by PVA, precursor reduction - NaBH4
•
metal particle size 2-4 nm
•
oxygen pressure 300 kPa, 30 - 50˚C, NaOH/glycerol = 4
Catalyst
1 wt.% Pd/C
1 wt.% Pd/C
Reaction
Conversion [%]
temperature [C ]
30
50
30
90
50
50
50
90
GLYA
88,3
64,0
80,6
37,9
Selectivity [%]
TARA
11,2
24,8
14,4
29,6
TOF [h-1]
GLYC
0,4
7,6
2,7
23,9
514
1151
Alardin (2001)
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Bi-promoted Pd catalysts – oxidation of polyols
•
great activity and selectivity of Pd-Bi/C catalysts in oxidation reaction of
polyols (spec. glyoxal acid)
Karski (2003)
•
cat. 5 wt.%Bi - 5 wt.%Pd/C
•
high activity and selectivity for oxidation of glucose
•
strong synergic effect between Pd and Bi
•
selectivity to gluconic acid 90% at 80% conversion
Prati (2007)
Catalyst preparation:
1.
Au/C: imobilization from PVA solution + reduction with 0,1M NaBH4
2.
Au-Pd/C: imobilization Au/C with Na2PdCl4 solution in pres. of PVA
•
metal particle size 3 - 4 nm
•
oxygen pressure 300 kPa, 50˚C, NaOH/GLY = 4
•
Selectivity to GLYA 80% at 50% conversion of GLY
Oxidation of secondary alcohol groups
of glycerol
◦
◦
◦
◦
dihydroxyacetone
acid region, pH = 1,5-3
catalysts based on Pt, Pt-Bi, Pt-Au
support: active carbon
P. Gallezot, Catalysis Today, 37 (1997) 414-416.
H. Kimura, Applied Catalysis A: General, 105 (1993) 147-158.
D. Liang, S. Cui, J. Gao, J. Wang, P. Chen, Z. Hou, Journal of catalysis, 32 (2011) 1831-1837
Kimura (1993)
• cat. 1 wt.%Bi–5 wt.%Pt/C – yield of DHA 20% at 30% conversion of GLY
• cat. 0,6 wt.%Bi–3 wt.%Pt/C – yield of DHA 30% at conversion of GLY 40%
• Batch and fixed-bed reactor
Gallezot (1997)
• cat. 1 wt.%Bi-5 wt.%Pt/C
• yield of DHA 37%, conversion of GLY 80%
• batch reactor
W. B. Hu (2010)
• cat. 3 wt.% Pt-0.6 wt.% Bi supported on activated carbon
• 80°C, 3 bar and at an initial pH of 2
• selectivity to DHA of 60% at 80% glycerol conversion
• low glycerol oxidation rate (TOF=370 h-1)
Rodrigues (2011)
• cat. 1 wt.Au/MWCNT
• 60°C, 3 bar and at an initial pH of 2
• selectivity to DHA of 60% at 93% glycerol conversion
• glycerol oxidation rate (TOF) = 4240 h-1
Aim of work
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Preparation of catalysts based on palladium loaded on different
type of polymeric support
Modification of catalysts by promoters, especially bismuth
Study reaction conditions – effect on the catalytic activity
Physico-chemical characterisation of catalysts
Study the performance of the catalysts in different types of
reactors
Optimization of reaction conditions with regard to maximizing the
yield of the desired products of mono-and dicarboxylic acids and
DHA
Study the catalytic performance of the catalysts for the oxidation of
various polyols
Experimental
Catalyst preparation
 microporous gel-type resin
 macroporous ion-exchange resin
 metallated by ion exchange method
 reduced with sodium borohydride or H2
Analysis of reaction mixture
HPLC:
 column - Alltech OA-1000
 detectors:
• SPD 10AVp
• RID-10A
semi-batch glass reactor
jacketed tubular glass
The preliminary results
Influence of support type

The Pd-Bi particles supported onto microporous gel-type resin showed better
catalytic performance than those supported onto macroporous resins
Conversion, selectivity [%]
100
80
60
40
20
0
TARA
GLYA
GLY
FB
B
SD2
B
FB
Dowex66
B
FB 50°C
FB 40°C
Dowex 1x4
Influence of metal content in batch
reactor
Higher content of metal in molar ratio Pd:Bi of 3:1 increased conversion of GLY
 No significant differences between reduction with NaBH4 and H2 was observed
Conversion, selectivity [%]

90
80
70
60
50
40
30
20
10
0
NaBH4
0,6:2
H2
NaBH4
1:1
H2
NaBH4
H2
1:0,3
TARA
GLYA
GLY
Pd:Bi
NaBH4
2:0,6
H2
NaBH4
H2
3:1
Influence of metal content in fixedbed reactor
Molar ratio and content of metals loaded on support strongly influenced the activity
and selectivity of the catalysts in both batch and fixed bed reactors
Conversion, selectivity [%]

100
90
80
70
60
50
40
30
20
10
0
TARA
GLYA
GLY
0,6:2
1:1
1:0,3
Pd:Bi
2:0,6
3:1
Thank you for your attention
This work was supported by the Slovak Research and
Development Agency under the contract No. APVV0133-11 and ERDF under the contract No.
HUSK/1101/1.2.1/0318