Esterification of acidic oils: a way towards new products for the biorefinery
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Esterification of acidic oils: a way towards new Esterification of acidic oils: a way towards new products for the biorefinery products for the biorefinery CNR ISTM, via G. Venezian 21, I-20133 Milano e-mail:[email protected] Federica Zaccheria, Simona Brini, Rinaldo Psaro, Carine Chan-Thaw and Nicoletta Ravasio Why Esters? Deacidification and Esterification over Silica - Zirconia Conclusions Transesterification and Esterification of olive acidic oils Ve.Li.Ca Project Oil Starting acidity Final acidity Conv % Jatropha Curcas (degummed) 0.84 0.18 78 1% oleic acid in rapeseed 0.98 0.16 84 3% oleic acid in rapeseed 3.33 0.27 92 Tobaccoseed 3.33 0.50 90 5% oleic acid in rapeseed 5.64 0.32 94 13% oleic acid in rapeseed 12.85 0.39 97 20% oleic acid in rapeseed 19.60 0.59 97 Olive Acidic Oils 53.67 7.44 86 Palm Fatty Acid Distillates 94.60 9.90 90 Tall Oil 98.10 8.53 91 Chicken fat 18.60 2.50 87 Animal fat 1 (cow, pig, chicken, sheep) 9.30 1.26 86 Animal fat 2 (cow and pig) 7.10 1.44 80 Transesterification + Esterification ofAcidic O ils 0 20 40 60 80 100 2 3 % mo TG FFA DG MG FAM E Starting m aterial First run – 1 h Second run – 1 h ESTERS Methylesters for fuels Triesters as lubricant s Methylesters as products (soap, paint and varnish, resins, solvents…) Esters with sterols as food additives Esters with sorbitol as surfactants •Because of the new European directive, only biofuels produced from non-food and secondary raw materials are permitted. • In homogeneous alkaline conditions, transesterifcation of unrefined or crude oils containing more than 5 wt.% of free fatty acids (FFA) is not allowed because of soap formation (use of basic catalysts). Need of acid catalyzed pretreatments: Esterification with sulfuric acid and sulfonic resins to make methylesters. Corrosive and costly! •Followed by transesterification of the triglycerides (TG) in homogeneous basic conditions. However, separation from the undesired products is difficult and costly Introduction Successful deacidification of different natural oil: from 20 to less than 1 wt% of FFA Able to esterify secondary raw materials Good results can be explained by the best trade-off among the Lewis acidity and surface –OH concentration features • Lewis-acid catalysts have been shown to carry out both the transesterifcation of TG and the esterification of FFAs [1, 2], although their activity could be inhibited by H 2 O formed during the esterification process. Silica alumina (SiAl) and silica zirconia (SiZr) are active in acid-catalyzed reactions. • SiZr, a Lewis-acid catalyst, is shown here to promote esterification of FFAs and concomitantly transesterifcation of TGs into methylesters. Esterification of acidic oils over a commercial silica zirconia catalyst eliminates the use of mineral acids in the pre-treatement. Moreover, after the treatment about 50% of the oil is already converted in methylesters, thus allowing one to reduce the amount of catalyst in the homogeneous, basic catalyzed, transesterification step, with the great advantage of minimizing the purification processes. SiO 2 - ZrO 2 active in both esterification and transesterifcation of low grade and waste oils No need to remove the in situ formed water [3] •Fulfill EN14214 regulation for biodiesel with 97.2% of FAME (for ester and monoglycerides) Our project in biorefinery Biolubricants Polyols ω-3 IBC IBBA Genotype selectio n IBC Proteic hydrolisate Biomass ICRM Oligomers and carbohydrates Oil Pressing ISTM Glycerol ISMAC Biopolymers Packaging ISMAC Scutching Fibre Ve.Li.Ca. Project on Hemp and Flax Biorefinery Experimenta l Material: SiO 2 -ZrO 2 has a SSA of 304 m 2 g -1 and a PV of 1.62 mL g -1 . Calcination at 270 °C for 30 min in air and under vacuo for 30 min Transesterification and deacidification: SiO 2 -ZrO 2 /oil= 1/10 wt.; MeOH/oil = 10/1 mol.; 180 °C, 1h, stainless steel autoclave Analysis: Agilent 7890N GC with a flame ionisation detector. Fatty mixtures were derivatized using N,O-bis (trimethylsylil)trifluoroacetamid e (BSTFA) together with a standard mixture comprising C19:0 methylester, mono-, di- and triglycerides [1] R. Psaro, M.N. Ravasio, F. Zaccheria, European Patent Application EP 07425579.5 (2007); PCT/EP2008/062255; WO2009037226 A1 [2] F. Zaccheria, S. Brini, R. PSaro, N. Scotti, N. Ravasio ChemSusChem, 2 (2009) 535 – 5372 SiO 2 - ZrO 2 active in both esterification and transesterification of low grade and waste oils SiO2- ZrO2 is a promising catalyst for the production of biofuels from low and very low grade oils [3] K. Suwannakarm, E. Lotero, K. Ngaosuwan, J.G. Goodwin, Ind. Eng.Chem. Res. 48 (2009) 2810 www.velica.org COST Action CM 0903 (UBIOCHEM ) COST Action CM 0903 (UBIOCHEM ) Acknowledgeme nts European Commission (ERIC) , Regione Lombardia and ENI are acknowledged for the funding of this work.
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IBC. Proteic hydrolisate. Biolubricants Polyols. Glycerol. Biopolymers. ISMAC. ESTERS. Packaging. Scutching. Fibre. Biomass. ISMAC. Oligomers and carbohydrates. ICRM. Triesters as lubricants. Esters with sterols as food additives. Esters with sorbitol as surfactants. - PowerPoint PPT Presentation
Transcript of Esterification of acidic oils: a way towards new products for the biorefinery
Esterification of acidic oils: a way towards new Esterification of acidic oils: a way towards new products for the biorefineryproducts for the biorefinery
CNR ISTM, via G. Venezian 21, I-20133 Milano
e-mail:[email protected]
Federica Zaccheria, Simona Brini, Rinaldo Psaro, Carine Chan-Thaw and Nicoletta Ravasio
Why Esters?
Deacidification and Esterification over Silica - Zirconia
Conclusions
Transesterification and Esterification of olive acidic oils
Ve.Li.Ca Project
Oil Starting acidity
Final acidity
Conv %
Jatropha Curcas (degummed) 0.84 0.18 78
1% oleic acid in rapeseed 0.98 0.16 84
3% oleic acid in rapeseed 3.33 0.27 92
Tobaccoseed 3.33 0.50 90
5% oleic acid in rapeseed 5.64 0.32 94
13% oleic acid in rapeseed 12.85 0.39 97
20% oleic acid in rapeseed 19.60 0.59 97
Olive Acidic Oils 53.67 7.44 86
Palm Fatty Acid Distillates 94.60 9.90 90
Tall Oil 98.10 8.53 91
Chicken fat 18.60 2.50 87
Animal fat 1 (cow, pig, chicken,
sheep)
9.30 1.26 86
Animal fat 2 (cow and pig) 7.10 1.44 80
Transesterification + Esterification of Acidic Oils
0
20
40
60
80
100
1 2 3
% m
ol
TG
FFA
DG
MG
FAMEStarting material First run – 1 h Second run – 1 h
ESTERS
Methylesters for fuels
Triesters as lubricants
Methylesters as products (soap, paint and varnish, resins,
solvents…)
Esters with sterols as
food additivesEsters with
sorbitol as surfactants
•Because of the new European directive, only biofuels produced from non-food and secondary raw materials are permitted.
• In homogeneous alkaline conditions, transesterifcation of unrefined or crude oils containing more than 5 wt.% of free fatty acids (FFA) is not allowed because of soap formation (use of basic catalysts). Need of acid catalyzed pretreatments: Esterification with sulfuric acid and sulfonic resins to make methylesters. Corrosive and costly!
•Followed by transesterification of the triglycerides (TG) in homogeneous basic conditions. However, separation from the undesired products is difficult and costly
Introduction
Successful deacidification of different natural oil: from 20 to less than 1 wt% of FFA
Able to esterify secondary raw materials Good results can be explained by the best trade-off among the Lewis
acidity and surface –OH concentration features
• Lewis-acid catalysts have been shown to carry out both the transesterifcation of TG and the esterification of FFAs [1, 2], although their activity could be inhibited by H2O formed during the esterification process. Silica alumina (SiAl) and silica zirconia (SiZr) are active in acid-catalyzed reactions.
• SiZr, a Lewis-acid catalyst, is shown here to promote esterification of FFAs and concomitantly transesterifcation of TGs into methylesters.
Esterification of acidic oils over a commercial silica zirconia catalyst eliminates the use of mineral acids in the pre-treatement. Moreover, after the treatment about 50% of the oil is already converted in methylesters, thus allowing one to reduce the amount of catalyst in the homogeneous, basic catalyzed, transesterification step, with the great advantage of minimizing the purification processes.
SiO2- ZrO2 active in both esterification and transesterifcation of low grade and waste oilsNo need to remove the in situ formed water [3]
•Fulfill EN14214 regulation for biodiesel with 97.2% of FAME (for ester and monoglycerides)
Our project in biorefinery
Biolubricants
Polyols
ω-3IBC
IBBA
Genotype selection
IBC
Proteic hydrolisate
Biomass
ICRMOligomers and carbohydrates
Oil
Pressing
ISTM
Glycerol
ISMAC Biopolymers
Packaging
ISMAC
ScutchingFibre
Ve.Li.Ca. Project on Hemp and Flax Biorefinery
ExperimentalMaterial: SiO2-ZrO2 has a SSA of 304
m2g-1 and a PV of 1.62 mL g-1. Calcination at 270 °C for 30 min in air and under vacuo for 30 min
Transesterification and deacidification: SiO2-ZrO2/oil= 1/10
wt.; MeOH/oil = 10/1 mol.; 180 °C, 1h, stainless steel autoclave
Analysis: Agilent 7890N GC with a flame ionisation detector. Fatty mixtures were derivatized using N,O-bis (trimethylsylil)trifluoroacetamide (BSTFA) together with a standard mixture comprising C19:0 methylester, mono-, di- and triglycerides
[1] R. Psaro, M.N. Ravasio, F. Zaccheria, European Patent Application EP 07425579.5 (2007); PCT/EP2008/062255; WO2009037226 A1
[2] F. Zaccheria, S. Brini, R. PSaro, N. Scotti, N. Ravasio ChemSusChem, 2 (2009) 535 – 5372
SiO2- ZrO2 active in both esterification and transesterification of low grade and waste oils SiO2- ZrO2 is a promising catalyst for the production of biofuels from low and very low grade oils
[3] K. Suwannakarm, E. Lotero, K. Ngaosuwan, J.G. Goodwin, Ind. Eng.Chem. Res. 48 (2009) 2810
www.velica.org
COST Action CM0903 (UBIOCHEM)1st Workshop, Córdoba (Spain), 13-15th May, 2010
COST Action CM0903 (UBIOCHEM)1st Workshop, Córdoba (Spain), 13-15th May, 2010
AcknowledgementsEuropean Commission (ERIC) , Regione Lombardia and ENI are
acknowledged for the funding of this work.
