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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