BIOCATALYTIC PROCESSES FOR THE PRODUCTION OF FATTY ACID ESTERS
BREW-Symposium11 May, 2005, Bioperspectives 2005
M. VICENTE, J. ARACIL AND M. MARTINEZ*CHEMICAL ENGINEERING DEPARTMENT. COMPLUTENSE UNIVERSITY. 28040 MADRID
E-MAIL: [email protected]
GREEN TECHNOLOGY AND SUSTAINABLE DEVELOPMENT
• USING OF RENEWABLE RAW MATERIALS
• SETTING UP NEW INTEGRATED PROCESSES. USE OF SELECTIVE CATALYSTS. AVOIDANCE OF POLLUTANTS AND BY-PRODUCTS
• NEW PRODUCT AND PROCESS DESIGN IN ORDER TO MINIMIZE WATER AND ENERGY WASTE.
PROCESSES FOR ESTER PRODUCTIONRAW MATERIALSESTER PRODUCTION PROCESSES
GENERAL SCHEMEESTERIFICATION & TRANSESTERIFICATION: CATALYST1). ESTERS OF MONOALCOHOLS
- Reaction study for different catalyst systems- Proposed schemes for oleyl oleate production
2). MONOGLYCERIDES- Reaction study for different catalyst systems- Proposed schemes for glycerol monooleate and
monoricinolate production
RAW MATERIALSRAW MATERIALS
OILS
HYDROLYSIS230ºC and 32 atm
TRANSESTERIFICATIONwtih Metanol
50ºC and basic catalyst
CRUDEFATTY ACIDS
CRUDEGLYCERINE
METHYL FATTYESTERS
HYDROGENATION225ºC and 50atm
FATTY ALCOHOLS
TRYGLYCERIDES TO OLEOCHEMICALS
SEPARATION DISTILLATIONHYDROGENATIONFRACTIONAL DISTILLATION
REFINING REFINEDGLYCERINE
DISTILLEDFATTY ACIDS
SATURATEDFATTY ACIDS
FRACTIONATEDFATTY ACIDS
UNSATURATEDFATTY ACIDS
OIL SOURCE C14 C16 C18 C18:1 C18:2 C18:3
Olive 0-1 7-15 1-2 70-85 4-12 -
Pits of olives - 4-6 2-4 75-85 4-10 -
Peanut - 12-15 14-16 54-76 12-25 -
Almond - 5-8 - 75-80 2-4 -
Tea 0-1 7-8 0-1 83-85 22-24 -
Hazelnut 0-1 2-4 1-2 90-95 2-3 -
Soya 0-1 7-10 3-6 25-35 52-60 2-6
Corn - 7-8 2-4 45-50 40-45 5-10
Laurel fruit 20-22 1-2 - 60-65 12-15 -
Laurel cherry 1-2 6-9 1-2 70-75 12-14 -
Cashew nut - 6-7 11-12 74-75 7-8 -
High oleic sunflower - 4 3 70-80 15-20 -
High oleic rapeseed 2 - 2 70-80 15-20 2
COMPOSITION OF MAIN OILSFOR OLEIC ACID PRODUCTION
ESTER PRODUCTION ESTER PRODUCTION PROCESSESPROCESSES
BIODEGRADABLE PRODUCTS
NON-FOODAGRICULTURAL
PRODUCTIONOIL SEEDS
OILS
FATTY ACIDS
ALCOHOLS
TRANSESTERIFICATION
ESTERIFICATION
ESTERS OF MONOALCOHOLS
MONOGLYCERIDES
GLYCERINE
ESTERIFICATION
ESTERIFICATION
DIGLYCERINE
POLYGLYCEROLESTERS
TRANSESTERIFICATION BIODIESEL
GENERAL REACTION SCHEMESGENERAL REACTION SCHEMES
A.) ESTERIFICATION PROCESS
R1-COOH + R2-OH R1-COO-R2 + H2OFATTY ACID ALCOHOL ESTER WATER
B.) TRANSESTERIFICATION PROCESS
CO-O-R1 CH2-OH CH2-OH
CO-O-R1’ + 2 CH-OH 3 CH-OH
CO-O-R1’’ CH2-OH CH2-O-OC-R1
OIL GLYCEROL MONOGLYCERIDE
CATALYTIC SYSTEMSCATALYTIC SYSTEMS
CONVENTIONAL PROCESSESHETERO-GENEOUS CATALYST
ENZYMATIC CATALYST
ACID CATALYST BASIC CATALYST
ESTERIFICATIONPROCESSES
Strong mineral acidsOrganic acidsIon exchange resinsMetal chlorides
Acid zeolites Free lipasesImmobilized lipases
TRANSESTERIFICATIONPROCESSES
Sulphuric acidChlorhydric acid Phosphoric acid
Alkaline hydroxidesAlkaline alkoxidesCarbonates
Anionic Exchange Resins: Oxides and Mixed Oxides (CaO-MgO)
Free lipasesImmobilized lipases
ADVANTAGES OF ENZYMATIC PROCESSES
• SIMPLER PROCESS SCHEMES• HIGHER SELECTIVITY• LESS WASTE• LOWER TEMPERATURE• LOWER PRESSURE• LOWER (DIRECT) PROCESS ENERGY REQUIREMENTS
1)1). . ESTERS OF MONOALCOHOLSESTERS OF MONOALCOHOLS
CATALYTIC ESTERIFICATION REACTION
CH3-(CH2)7 - CH = CH -(CH2)7- COOH
OLEIC ACID
+ R-CH2 - OH
ALCOHOL
CH3-(CH2)7 - CH = CH - (CH2)7 -COO-CH2-R
ESTER
H2O
WATER
+
CATALYST
OLEYL OLEATE PRODUCTIONOLEYL OLEATE PRODUCTION
R = CH3-(CH2 )7 - CH = CH -(CH2 )7- OLEYL ALCOHOL
COMPARISON BETWEEN DIFFERENT CATALYTIC SYSTEMS FORESTERIFICATION REACTION OLEIC ACID + OLEYL ALCOHOL
Molar ratio [AC]:[Al] = 1:1Constant temperatureConstant working pressureReaction time: 2h
BatchReactor
OLEIC ACID
OLEYL ACOHOL
VACUUM PUMP
ESTER
WATER
Catalytic system T (ºC) Catalyst
(wt%)P
(mmHg)Ester
yield (%)
SnCl2 164 0.45 579 55
Y-Zeolite 180 0.60 160 47
ImmobizedEnzyme 70 5 60 95
95,5 94,9 95,6
30,5
88,1 90,7 92,01
51,7
0
10
20
30
40
50
60
70
80
90
100
LIP-IM20 LIP-IM50 LIP-IM LIP-10 SP-A SP-B NOVO SnCl2
Different enzymatic system comparison
REACTION CATALYST %wt cat. XAC
LIP-IM20 Lipozyme IM20 5 95,5
LIP-IM50 Lipozyme IM50 5 94,9
LIP-IM Lipozyme IM 5 95,6
LIP-10 Lipozyme 10,000 5 30,5
SP-A SP-435-A 5 88,1
SP-B SP-435-B 5 90,7
NOVO Novozyme435 5 92,01
SnCl2 SnCl2.5H2O 1 51,7
Operation conditions:- Molar ratio [AC]/[AL] 1:1- Temperature 70ºC- Pressure 60 mmHg(except LIP-10, P=710mmHG)- Reaction time: 2 h
COMPARISON BETWEEN DIFFERENT ENZYMATIC SYSTEMS FORESTERIFICATION REACTION: OLEIC ACID + OLEYL ALCOHOL
PROPOSED SCHEMESFOR OLEYL OLEATE PRODUCTION
UCM in collaboration with Dr. Michel Poulina (Uniquema)
OLEYL OLEATE PRODUCTION
OLEIC ACID OLEYL ALCOHOL OLEYL OLEATE
Technical grade (90%) Technical grade (90%) Acid value <1Hydroxyl value < 30
RAW MATERIALS PRODUCT
PROPOSED SCHEMES FOR OLEYL OLEATE PRODUCTION
PRODUCTION REACTOR CATALYST
CONVENTIONAL BATCH STIRRED TANKp-toluenesulfonic acidTin chlorideZeolites
BIOPROCESS BATCHSTIRRED TANKFIXED-BED
Immobized lipaseImmobized lipase
BATCH REACTOR130ºC, Patm
0.6%wt cat; 16 h
OLEIC ACIDtechnical grade
OLEIC ALCOHOLtechnical grade
NEUTRALIZATIONDECANTATION
WASHINGDECANTATATION
BLEACHINGClays
CATALYSTp-toluenesulfonic acid
DESODORIZATIONStripping
80ºC, 10 mbar
CENTRIFUGATIONACIDULATION
H2SO4 /ACID RECOVERY
STEAMPRODUCTION
DRYING
OLEYL OLEATE PRODUCTION BATCH_STIRRED TANKNon-enzymatic esterification: p-toluenesufonic acid
NaOH, solution
Water phase
Water
Soap
OLEIL OLEATE
Water phase
OLEYL OLEATE PRODUCTION BATCH_STIRRED TANKEnzymatic esterification: immobilized lipases
BATCH REACTOR60ºC, 100mbar1.5%wt cat; 15h
ENZYME RECYCLE
FILTRATION60ºC, Patm
Condensation
DEODORIZATIONStripping
80ºC, 10 mbar
DRYING
STEAMPRODUCTION
CleanEnzyme
OLEIC ACIDtechnical grade
OLEIC ALCOHOLtechnical grade
OLEYL OLEATE
WATER
DEODORIZATIONStripping
80ºC, 10 MBAR
DRYING
FIXED-BEDREACTOR60ºC, Patm
FLASH SEPARATOR
80ºC, P?
TANK
UNIT 1
STEAMPRODUCTION
TANK
OLEYL OLEATE PRODUCTION BATCH_FIXED BEDEnzymatic esterification: immobilized lipases
OLEIC ALCOHOLtechnical grade
OLEIC ACIDtechnical grade
OLEYL OLEATE
WATER
CATALYST REACTIONCONDITIONS
DOWNSTREAM PROCESSES
REFINED PROCESSES
ACID CATALYST
130ºCAtmospheric pressure0.6 %wt catalyst
1. NEUTRALIZATION2. WASHING3. CENTRIFUGATION
1. BEACHING2. DEODORIZATION3. DRYING
IMMOBILIZEDLIPASESSTIRRED TANK
60ºC100 mbar1.5 %wt catalyst
1. FILTRATION2. ENZYME RECOVERY
1. DEODORIZATION2. DRYING
IMMOBIZEDLIPASESFIXED-BED
60ºCAtmospheric pressure
1. FLASH DISTILLATION
1. DEODORIZATION2. DRYING
PROCESS COMPARISON – OLEYL OLEATE
Conventional and enzymatic process designs are roughly comparable.
Outcome of energy analysis (including energy to produce the catalysts used):
ENERGY ANALYSIS – OLEYL OLEATE
ECONOMICS – OLEYL OLEATE
0
100
200
300
400
500
600
700
800
10 100Capacity in in kt p.a.
Brea
keve
n en
zym
e co
st*)
Enzymatic, stirred tank Enzymatic, fixed bedLipozyme RM IM Lipozyme TM IM
Lipozyme RM IM
Other commercially available enzyme:- novozymes 435: 1500 EUR/kg
*) Breakeven enzyme cost: Enzyme costs below the broken line are economically viable.
Lipozyme TM IM
O:\WPs\WP3(Envir)\BrewTool\BackgroundTables\Enzymes\Oleyl_oleate_COMPAR_CAT.xls
2)2). . MONOGLYCERIDESMONOGLYCERIDES
CATALYTIC TRANSESTERIFICACION REACTION SCHEME
CATALYST
MONOGLYCERIDE OLEATE PRODUCTIONMONOGLYCERIDE OLEATE PRODUCTION
TRYGLYCERIDE + 2 GLYCEROL 3 MONOGLYCERIDE
2 TRYGLYCERIDE + GLYCEROL 3 DIGLYCERIDES
CATALYST
COMPARISON BETWEEN DIFFERENT ENZYMATIC SYSTEMS FORESTERIFICATION REACTION: OLIVE OIL + GLYCEROL
517
87
2
23
27
48
2
33
31
34
518
86
517
87
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Oil NOV 3h NOV 7h LIP 3h LIP 7h
Final product composition for different enzymes
Triglycerides Diglycerides Monoglycerides Fatty acids
CATALYST t (h) FFA MG DG TG
Olive oil 0 5 1 7 87
Novozyme 435 3 2 23 27 48
Novozyme 435 7 2 33 31 34
Lipozyme IM 3 5 1 8 86
Lipozyme IM 7 5 1 7 87
Reference: Martinez, M. Coterón, A. and Aracil, J.Reactions of Olive Oil and Glycerol over Immobilized LipasesJAOCS, vol. 75, no.5 (1998)
PROPOSED SCHEMESFOR MONOGLYCERIDES
PRODUCTION
UCM in collaboration with Dr. Michel Poulina (Uniquema)
MONOGLYCERIDES PRODUCTION
SUNFLOWER OIL GLYCEROL RICINOLEIC ACID
High oleic sunflowerOleic acid > 80%
Glycerine(Refined grade)
Technical grade (80%)
RAW MATERIALS PRODUCT
PROPOSED SCHEMES FOR MONOGLYCERIDES PRODUCTION
REACTION REACTOR CATALYST
CONVENTIONAL TRANSESTERIFICATION STIRRED TANKKOHNaOH
BIOPROCESSTRANSESTERIFICATIONESTERIFICATION
BASKET REACTORSTIRRED TANK
Immobilized lipasesImmobilized lipases
HIGH GRADE PRODUCT
LOW GRADE PRODUCT
90-96 MG1-5 DG< 1 TG< 1 Glycerol< 1 Fatty acids
35-60 MG35-60 DG1-20 TG1-20 Glycerol1-10 Fatty acids
GLYCEROL MONOOLEATE PRODUCTION BATCH_STIRRED TANKNon-enzymatic transesterification: Basic catalyst
HOSO
GLYCEROL
MIXER
REACTOR (2 steps)1. Reaction: 180ºC, Patm
NaOH 0.2wt%2.Flash distillation: 100mbar
DECANTATION50ºC, Patm
CONDENSATION
WASHING50ºC, Patm
SHORT PATH DISTILLATION200ºC, P <1 mbar
KOH
To glycerol feed
From condensation
NaOH
GLYCEROLPURIFICATION
Water
DYGLYCERIDEResidue
MIXER
Waterphase
HQ MONOOLEATE LQ MONOOLEATE
HOSF
GLYCEROL
MIXER50ºC, Patm
BASKETREACTOR60ºC, Patm
1.5%wt cat, 2 h
CRYSTALLIZATION 160ºC-27ºC0.06ºC/min
CRYSTALLIZATION 250ºC-32ºC0.04ºC/min
CRYSTALLIZATION 345ºC-35ºC
0.02 ºC/min
TANK
HQ MONOOLEATE
LQ MONOOLEATE
GLYCEROL MONOOLEATE PRODUCTION BATCH_BASKET REACTOREnzymatic transterification: Immobilized lipases
GLYCEROL MONORICINOLATE PRODUCTION BATCH_STIRRED TANKEnzymatic esterification: Immobilized lipases
RICINOLEICACID
GLYCEROL MIXERBATCH REACTOR
60ºC, 100mbar3wt% cat, 4h
FILTRATION40ºC
CENTRIFUGATION40ºC
ADSORPTION40ºC
ENZYMERECOVERY
GYCEROLRECOVERY
CONDENSATION
Enzymefeed
DRYING
DEODORIZATION40ºC
Resins
GLYCEROLMONORICINOLATE
STEAMPRODUCTION
PROCESSESREACTIONCONDITIONS
DOWNSTREAM PROCESSES
REFINED PROCESSES
TRANSESTERIFICATIONBASIC CATALYSIS(Glycerol monooleate)
180ºCAtmospheric pressure0.2 %wt catalyst
1. DECANTATION2. WASHING
1. SHORT PATH DISTILLATION
TRANSESTERIFICATIONENZYMATIC CATALYSIS(Glycerol monooleate)
60ºCAtmospheric pressure1.5 %wt catalyst
CRYSTALLYZATION(3 STEPS)
1.DEODORIZATION2.DRYING
ESTERIFICATIONENZYMATIC CATALYSIS(Glycerol monoricinolate)
60ºC100 mbar3 %wt catalyst
1.FILTRATION2.CENTRIFUGATION3. ADSOPTION
1.DEODORIZATION2.DRYING
PROCESS COMPARISON - MONOGLYCERIDES
Outcome of energy analysis: analogous to oleyl oleate
ENERGY ANALYSIS - MONOGLYCERIDES
ECONOMICS – GLYCEROL MONOOLEATE
0
20
40
60
80
100
120
10 100Capacity in in kt p.a.
Brea
keve
n en
zym
e co
st*)
Batch esterification Batch transesterificationLipozyme TM IM
Lipozyme TM IM
Other commercially available enzymes:- novozymes 435: 1500 EUR/kg- Lipozymes RM IM: 600 EUR/kg- Lipozymes TM IM: 75 EUR/kg
*) Breakeven enzyme cost: Enzyme costs below the broken line are economically viable.
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CONCLUSIONS
• KEY PROCESS ADVANTAGES: HIGHER SELECTIVITY, LESS WASTE; LOWER TEMPERATURE AND LOWER PRESSURE
• SMALL IMPROVEMENT POTENTIALS FOR ENERGY AND GHG EMISSIONS• BREAK-EVEN ENZYME COST CAN BE REDUCED BY UP TO FACTOR 3 BY
ECONOMIES OF SCALE• ALLOWABLE ENZYME COST UP TO FACTOR 5 BY PROCESS
IMPROVEMENT• ENZYME COSTS FOR SMALL SCALE NEED TO DROP TO AROUND 100
EUR/KG,FOR LARGE SCALE A FEW TENS OF EUROS/KG
• SYNERGY OF WHITE BIOTECHNOLOGY AND PROCESS IMPROVEMENTS
SUBSTANTIAL IMPROVEMENTS ESP. IN IN ECONOMICS