Development of catalysts for glycerol esterification
Institute of Organic Chemistry with Center of Phytochemistry
COST Action TD1203: Food waste valorization for sustainable chemicals, materials & fuels (EUBis)
Biorefinery for the Production of Energy and Bio-based Products
Turin, 29-30 October 2013
COST TD1203WG3 Chemical Processing
BULGARIAN ACADEMY OF SCIENCESInstitute of Organic Chemistry with Center of Phytochemistry
Margarita Popovahttp://www.orgchm.bas.bg/
Research activities:
Synthesis• Micro- and Mesoporous materials – MCM-41, SBA-15, SBA-16, zeolites, mesoporous carbons etc.
•Modification of Micro- and Mesoporous materials with organic functional groups or metal oxides
• Nanosized mesoporous metal oxides (supported or not supported)
Heterogenous catalysis• Glycerol esterification
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Earlier Glycerol industry (< 2004)
market
• Stable market – 1 Mio t/yr (USA)• Mostly from soap and fats splitting
• Food products • Personal care products• Tobacco and pharmaceuticals
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Biodiesel production process
Crude glycerol production more than double
1000 kg 100 kg 100 kg 1000 kg
World production: Approx. 15 Mio tones 1.5 Mio ton crude glycerol
Glycerin
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Crude glycerin
Crude glycerol purification
MONG – matter organic non-glicerol
Processes of catalytic conversion of glycerol into useful chemicals
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Glycerol esterification with acetic acid
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Homogenous catalysts
Heterogenous catalysts
Modified mesoporous silicas:
resins ( Amberlyst-15), active carbon, ZrO2, zeolites (USY, ZSM-5), niobic acid etc.
“green” chemical reaction
Nanosized mesoporous metal oxides:
Nanosized ZrO2, Nanosized ZrO2/CeO2Nanosized WO3/ZrO2
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Zeolites:
Mesoporous ZSM-5Nano BetaCuCLI
SBA-15, SBA-16, KIL-2, MCM-41
Modification of mesoporous silicates
SBA-15SBA-16KIL-2MCM-41
Post synthetic or direct synthesis
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SO3H –
ZrO2 –
Reaction conditions: 0.2 g catalyst, glycerol/acetic acid weight ratio = 1:10, reaction time = 3 h
Glycerol esterification on the sulphonic-functionalized mesoporous silicas
catalysts80 oC 100oC 130oC
MAG DAG TAG MAG DAG TAG MAG DAG TAG
SBA‐15SO3H 50.0 39.0 11.0 37.0 44.0 19.0 23.5 56.0 20.5
SBA‐16SO3H 54 33 13 48 36 16 35 47 18
KIL‐2SO3H 64 22 8 48 32 20 31 48 21
0
10
20
30
40
50
60
70
80
90
100
Con
vers
ion,
%
KIL-2SO3HSBA-15SO
3H SBA-16SO
3H
130oC130oC130oC100oC 100oC 100oC80oC80oC80oC
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76.5%
90 %
Influence of reaction time inglycerol esterification at 100 oC
Stability of the SBA-15SO3H catalystin glycerol esterification at 100 oC
1
2
30
20
40
60
MAG
TAG
DAG
conversion
wt.%
cycles
Glycerol esterification on sulphonic-functionalized mesoporous silicas
0 1 2 3 4 5 60
20
40
60
80
100
Con
vers
ion,
wt.%
Reaction time, hours
SBA-15SO3H SBA-16SO3H KIL-2SO3H
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0
10
20
30
40
50
60
70
80
90
100
SO 42- /12
ZrKIL
-2
SO 42- /12
ZrKIL
-2
SO 42- /12
ZrKIL
-2
4ZrK
IL2
SO 42- /4Z
rKIL
28Z
rKIL
-2
SO 42- /8Z
rKIL
-2
8ZrK
IL-2
4ZrK
IL2
SO 42- /4Z
rKIL
2SO 4
2- /8ZrK
IL-2
SO 42- /8Z
rKIL
-2
Con
vers
ion,
%
SO 42- /4Z
rKIL
2
60oC
12ZrK
IL-2
12ZrK
IL-2
80oC 100oC
Reaction conditions: 0.1 g catalyst, glycerol/acetic acid weight ratio = 1:10, reaction time = 3 h
Glycerol esterification on Zr-modified KIL-2 mesoporous silicas
catalysts60 oC 80oC 100oC
MAG DAG TAG MAG DAG TAG MAG DAG TAG
4ZrO2/KIL‐2 0 0 0 93.3 6.7 0 75.9 12.1 12.1
SO42‐4ZrO2/KIL‐2 84.6 15.4 0 66.2 24.3 9.5 23 58 19
8ZrO2/KIL‐2 0 0 0 86.7 13.3 0 63.4 26.8 9.9
SO42‐8ZrO2/KIL‐2 73.1 19.2 7.7 51.6 34.7 13.7 11 69 21
12ZrO2/KIL‐2 0 0 0 84.3 13.2 2.5 60.9 27.9 11.1
SO42‐12ZrO2/KIL‐2 77.3 17.1 5.5 32.3 49.0 18.7 2.7 77.1 20.1
100 %
97%
Glycerol esterification on Zr-modified SBA-15 mesoporous silicas
0
2 0
4 0
6 0
8 0
1 0 0
15ZrO 2/S
BA-15
8ZrO 2/S
BA-15
15ZrO 2/S
BA-15
8ZrO 2/S
BA-15
15ZrO 2/S
BA-15
Con
vers
ion,
%
8ZrO 2/S
BA-15
8 0 o C 9 0 o C 1 0 0 o C
Reaction conditions: 0.2 g catalyst, glycerol/acetic acid weight ratio = 1:10, reaction time = 3 h
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catalysts80 oC 90oC 100oC
MAG DAG TAG MAG DAG TAG MAG DAG TAG
8ZrO2/SBA‐15 86.7 9.8 3.5 72.7 19.7 7.6 52.9 32.9 14.2
15ZrO2/SBA‐15 89.8 8.3 1.9 79.8 16.5 3.8 61.6 28.0 10.4
47%
90 %
Calcination300-500°C
CTAB micellation
in H2O
ZrCl4 (CeCl2)in H2O+
aqueous ammoniato pH 10.5
Hydrothermaltreatment
100°C, 24 h
Minimiziation of defect sites by dissolution and reprecipitation that hinders grain growth during calcination
hydrous zirconiaprecipitation
nanosizedmesoporousZrO2ZrO2/CeO2
Preparation of nanosized mesoporous metal oxides
CTAB –N-Hexadecyl-N,N,N-trimethylammonium bromide
Mesoporous ZrO2 TD1203
Reaction conditions: 0.1 g catalyst, glycerol/acetic acid weight ratio = 1:10, reaction time = 3 h
Glycerol esterification on nanosized ZrO2 and ZrO2/CeO2
0
2 0
4 0
6 0
8 0
1 0 0
nanoW
O x/C
eO 2
nanoW
O x/C
eO 2
Con
vers
ion.
%
nanoZrO 2
/CeO 2
nanoZrO 2
/CeO 2
bulkZrO 2nan
oZrO 2
nanoZrO 2
bulkZrO 2
80 oC 100 oC
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catalysts80oC 100oC
MAG DAG TAG MAG DAG TAG
bulkZrO2 92.1 7.9 0 69.8 24.1 4.5
nanoZrO2 79.2 16.7 4.2 61.2 27.7 11.1
Nano CeO2/ZrO2 83.3 12.1 4.6 66.8 23.7 9.5
Nano WO3/ZrO2 73.9 17.4 8.7 60.5 27.2 12.3 39 %
90%
Reaction conditions: 0.1 g catalyst, glycerol/acetic acid weight ratio = 1:10, reaction time = 3 h
Glycerol esterification on nanosized ZrO2 and SO42-/ZrO2
0
1 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
1 0 0
SO 42- /nan
oZrO 2
Con
vers
ion,
%
SO 42- /bulkZrO 2
6 0 oC
SO 42- /bulkZrO 2
bulkZrO 2
nanoZrO 2
SO 42- /nan
oZrO 2
nanoZrO 2
SO 42- /bulkZrO 2
bulkZrO 2
SO 42- /nan
oZrO 2
8 0 oC 1 0 0 oC
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catalysts60 oC 80oC 100oC
MAG DAG TAG MAG DAG TAG MAG DAG TAG
bulkZrO2 0 0 0 92.1 7.9 0 69.8 24.1 4.5
SO42+bulkZrO2 87.8 12.2 0 55.6 32.1 12.3 10.7 76.1 13.2
nanoZrO2 0 0 0 79.2 16.7 4.2 61.2 27.7 11.1
SO42+nanoZrO2 86.1 12.0 1.9 50.7 32.7 16.6 4.1 75.5 20.4
96 %
100 %
Crude glycerol esterification with acetic acid
catalysts60 oC 80oC 100oC
MAG DAG TAG MAG DAG TAG MAG DAG TAG
CuCLI 80.3 19.7 0 84.1 13.3 2.6 52.2 35.7 12.2
SO42‐/12ZrO2KIL‐2 100 0 0 77.8 17.8 4.4 63.7 26.4 9.9
nanoZrO2 0 0 0 63.4 26.8 9.8 63.2 27.6 9.2
0102030405060708090
100
100oC80oC60oC100oC80oC60oC60oC 100oC
Con
vers
ion,
%
80oC
CuCLI SO42-/12ZrO2KIL-2
nanoZrO2
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Property %methanol 2.3glycerol 85.8MONG – matter organic non glycerol
11.9
Crude glycerol from biodiesel
Cu-ClinoptiloliteSO4
2-/12ZrO2KIL-2nanoZrO2
100 %
48 %
Pure and crude glycerol esterification on natural zeolite
catalysts60 oC 80oC 100oC
MAG DAG TAG MAG DAG TAG MAG DAG TAG
CuCLI (pure glycerol) 79.6 20.4 0 85.3 11.8 2.9 47.7 38.6 13.7
CuCLI (crude glycerol) 80.3 19.7 0 84.1 13.3 2.6 52.2 35.7 12.2
0
20
40
60
80
100
100oC80oC60oC60oC 100oC
Con
vers
ion,
%
80oC
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Property %methanol 2.3glycerol 85.8MONG – matter organic chompounds
11.9
Crude glycerol from biodiesel
Cu-Clinoptilolite
Concluding remarks
• Modified mesoporous silicas and nanosized mesoporous metal oxides arepromising heterogeneous catalysts for glycerol esterification with aceticacid. The catalysts show high catalytic activity and selectivity to di- and tri-acetylglycerols.
• The cheaper Cu-modified natural zeolite clinoptilolite appears more efficientin utilization of crude glycerol obtained in the production of biodiesel in thesame esterification reaction.
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Dr. Momchil DimitrovAssoc. Prof. Vesselina MavrodinovaAssoc. Prof. Pavletta ShestakovaInstitute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria
Assoc. Prof. Natasa Novak TusarDr. Alenka RisticNational Institute of Chemistry, Ljubljana, Slovenia
Assoc. Prof. Magdolna MihalyiAssoc. Prof. Agnes SzegediInstitute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest, Hungary
Acknowledgements
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