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Design of Bio -Based Solvents
Sophie THIEBAUD-ROUX,
M. Bergez-Lacoste, P. De Caro, J.F. Fabre, V. Gerbaud, Z. Mouloungui
Laboratoire de Chimie Agro-industrielle,Toulouse, FranceLaboratoire de Génie Chimique, Toulouse, France
Colloque franco-nordique Biomass Conversion : Green Chemistry & Innovative Processes (10-11 March 2016)
Fossil resources depletionVOCs emissions (≈ 20%), Flammable, ToxicRegulationsConsumers demand for safer and healthier productsOpportunity for companies to set themselves apartfrom the competition
Conventional Solvents Pharmaceutical industry,Cleaning, Paints, Extraction…
Why replacingconventional solvents?
1. IHS Chemical Special Report. 2013 Global solvents: Opportunities for greener solvent.
2. Agence de l’Environnement et de la Maitrise de l’Energie. Report. 2015. Marchés actuels des produits biosourcés et évolutions à horizons 2020 et 2030. 2
Worlwide consumption of solvents in 2012 : about 28 million metric tons (about 6 million in Europe)
Solvent consumption in France in 2012 :600 kt (5.8 % of bio-based solvents)
The market of bio-solvents in France is expected to increase from 35kt to 55kt in 2020.
Context : substitution of petrochemical solvents
Biosolvents
Context : substitution of petrochemical solvents
Criteria for the design of biosolvents
3
� Bio-based products obtained from renewable building blocks.
� Development of eco-friendly processes
� Reduced carbon footprint due to replacement of solvents from petrochemicalssources
� Technical specifications : performance for the targeted application and therequired safety properties (solubility, flammability…)
� Environmental and health properties : biodegradability, volatility, low eco-toxicity, non-carcinogenic…
� Eco-compatibility and efficiency of the process : abide by the 12principles of green chemistry
� Cost : competitive in terms of prices
Examples of commercialized bio -based solvents
Biosolvents
Organic acids esters Ethyl lactate…
TerpenesLimonene, terpineol…
Fatty acids estersMethyl or ethyl esters derived
from vegetable oil
AlcoholsBioethanol, butanol…
Glycerol derivativesGlycerol carbonate…
Furfural derivatives2-MeTHF…
Methodologies for the
substitution of
conventional solvents
• Trial and error• Predictive• Reverse design
5
Bio-based platformmolecule
Chemist knowledgeof chemical
transformations
Poo
l of d
eriv
edm
olec
ules
6
Chemist’s selection guided by his knowledgeabout :• industrially viable and environmentally acceptable
transformation processes• existing solvents classifications
Bio-based platformmolecule
1: Trial and errormethodologyChemist knowledge
of chemicaltransformations
Experimental evaluationwith targeted application
Poo
l of d
eriv
edm
olec
ules
Substitution methodology
Validation of candidates or further experiment
Synthesisof the molecules
7
Bio-based platformmolecule
1: Trial and errormethodologyChemist knowledge
of chemicaltransformations
Experimental evaluationwith targeted application
Poo
l of d
eriv
edm
olec
ules
Substitution methodology
Validation of candidates or further experiment
Synthesisof the molecules
8
� Time –consuming method� The selected solvent may not necessarily be the best alternative
Tools :
Bio-based platformmolecule
1: Trial and errormethodology
2: PredictiveMethodology
Prediction of properties and selection of candidates matching specifications
Chemist knowledgeof chemical
transformations
Experimental evaluationwith targeted application
Poo
l of d
eriv
edm
olec
ules
Substitution methodology
Validation of candidates or further experiment
Validation of candidates or further prediction
Synthesisof the molecules
9
Tools :
Bio-based platformmolecule
1: Trial and errormethodology
2: PredictiveMethodology
Prediction of properties and selection of candidates matching specifications
Chemist knowledgeof chemical
transformations
Experimental evaluationwith targeted application
Poo
l of d
eriv
edm
olec
ules
Substitution methodology
Validation of candidates or further experiment
Validation of candidates or further prediction
Synthesisof the molecules
10
� Only potentially interesting molecules are synthesized and tested� Time, energy and raw materials savings
Tools for predictive methodology
Tools Descriptions Developed by
HSPiP Hansen Solubility Parameters in Practice Steven Abbott, TCNF Ltd
COSMO-RS COnductor like Screening MOdel for Real Solvents Andreas Klamt, Cosmologic
SparcSparc Performs Automated Reasoning in Chemistry (vapor pressure, boiling point…)
EPA
IBSS InBioSynSolv Project InBioSynSolv, INPT
PBT Persistance, Bioaccumulation, Toxicity Communauté Européenne
Epi Suite Estimation Program Interface (Biodegradability, BCF and some physico-chemical properties)
Communauté Européenne
VEGAVirtual models for Evaluating the properties of chemicals within a Global Architecture (Toxicity)
EPA
Caesar Computer Assisted Evaluation of industrial chemical Substances According to Regulations
EPA
Tox predict Estimate toxicological hazard of a chemical structure EPA
Phy
sico
-che
mis
try
Toxi
city
/ Eco
toxi
city
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Bio-based platformmolecule
2: PredictiveMethodology
Prediction of properties and selection of candidates matching specifications
3: Reverse designGeneration of molecules
satisfying a set of requirementsdefined a priori
Chemist knowledgeof chemical
transformations
CAMD tool+
Substitution specifications
Experimental evaluationwith targeted application
Poo
l of d
eriv
edm
olec
ules
In s
ilico
cand
idat
es
Substitution methodology
Validation of candidates or further experiment
Validation of candidates or further prediction
Validation of the best candidates
or back to CAMD tool
Synthesisof the molecules
1: Trial and errormethodology
Virtual LaboratoryComputer-aided molecular designProject ANR INBIOSYNSOLV
IBSS
12
Reverse design using a CAMD tool
List of moleculesranked according to
their predictedperformances
IBSS
Synthons and building blocks
Plants
Technical and safetyspecifications :
target property values forphysico-chemical properties (T°, δd,p,h, Flash point, viscosity…)
Environmental and healthspecifications (due to regulatory constraints) :
volatility, toxicity, ecotoxicity, biodegradability…
Reverse design
13
Starting point for molecular architecture
IBSS Computer Aided Product DesignGeneration of molecules from a bio-based building block and elementary blocks by connecting them together
Resulting structures represented by a matrix (diagonal elements : group or fragment, off-diagonal elements : bond type connections
Each bio-based structure generated by IBBS undergoes the prediction of properties 14
IBSS Computer Aided Product DesignProperty calculation models
- 39 properties for pure substances, 10 for mixtures• Physico-chemical properties
Hansen solubility parametres, boiling and melting points, Vmolar, viscosity, vaporization enthalpy, Flash point, …
• Environnemental properties
BCF, LC50, log kow, vapor pressure
• 2 equilibrium properties (S/L, L/V)
Multi-objective CAPD problem :transformed into a single-objective problem aiming atmaximizing a global performance
- Function performance selected among :
Addition (gaussian function) ou product (desirability function)
Acentric Factor ...............................................................................
Enthalpy of vaporization at 298K ..........................................................Enthalpy of vaporization at the normal boiling point ................................
Enthalpy / Standard enthalpy of fusion ...................................................
Enthalpy / Standard enthalpy of formation at 298K ................................Entropy / Entropy of Melting ..............................................................
Entropy / Entropy of Vaporization at the normal boiling point ......................EHS / Acute Toxicity (96-h LC50) .......................................................
EHS / Aqueous Solubility ................................................................EHS / Bioconcentration Factor ............................................................
EHS / Environmental Impact index .......................................................
EHS / Environmental Waste index ......................................................
EHS / Health index ........................................................................EHS / Safety index .........................................................................
EHS / LCA index ..........................................................................EHS / Kow / Octanol - water partition coefficient ................................
Gibbs energy / Standard Gibbs energy at 298K .......................................
Solubility parameter / Hansen solubility parameter - dispersion (δD) ............
Solubility parameter / Hansen solubility parameter - Polar(δP) ...................
Solubility parameter / Hansen solubility parameter - H2-bond (δH) ..............
Solubility parameter / Hansen solubility parameter / HSP Distance ..............Solubility parameter / Hildebrand Solubility parameter .............................
Solubility parameter / RED – Relative Energy Difference ..........................
Heat capacity / Cp - Ideal gas ............................................................Pressure / Critical Pressure ..............................................................Pressure / Vapor Pressure ................................................................
Surface Tension at 298 K ................................................................
Surface Tension (as a function of temperature) ........................................Temperature / Auto ignition temperature .............................................
Temperature / Critical Temperature ...................................................
Temperature / Flash Point (in air at atmospheric pressure) .........................Temperature / Normal Boiling Point ...................................................
Temperature / Normal Melting Point ..................................................
Viscosity / Viscosity at 300 K ............................................................Viscosity / Liquid Viscosity as a function of temperature ...........................
Volume / Liquid molar volume as a function of temperature.......................Volume / Liquid molar volume at 298 K ..............................................
Volume / Critical Volume ................................................................
15
Bio-based platformmolecule
1: Trial and errormethodology
2: PredictiveMethodology
Prediction of properties and selection of candidates matching specifications
3: Reverse designSelection among the candidates
listed by the CAMD tool
Chemist knowledgeof chemical
transformations
CAMD tool+
Substitution specifications
Bio-basedsolvents
Poo
l of d
eriv
edm
olec
ules
In s
ilico
cand
idat
es
Substitution methodology
Time and cost savings
• Wide range of molecules• Prediction and comparison with
specifications made by software
16
Case studySubstitution of
conventional solvents
OO Furfural
Epoxy resinpre-polymers
cleaningPredictiveReverse design
17
• Bio-based platformmolecule: Furfural
> Available: annual global production 25.104 tons
> Produced by sugarsdehydration
> Obtained from agriculture co-products rich in pentosans: corncobs, bagasse…
> Platform for the production of furan, piperidine, furfurylalcohol…
• Epoxy resin pre-polymerscleaning
> Cleaning of manufacturingand conditioning materialsrequires conventionalsolvents: acetone, methylethyl ketone
> Alternative solvents to limitVOCs emissions
OO
BADGE TGPA
• Bio-based platformmolecule: Furfural
> Available: annual global production 25.104 tons
> Produced by sugarsdehydration
> Obtained from agriculture co-products rich in pentosans: corncobs, bagasse…
> Platform for the production of furan, piperidine, furfurylalcohol…
• Epoxy resin pre-polymerscleaning> Specifications defined to meet
industrial needs
> Specifications used as inputs in IBBS Tool
OO
Property Specification
Technical performanceMelting point < 0°CBoiling point 100°C <...< 250°C
SolubilityHansen parameters TGPA δD=17,4 , δP=6,1, δH=6,4
radius: 12,38Safety
Flash point > 61°Clog Kow < 3
EnvironmentVapour pressure < 10Pa, 20°CBioaccumulation BCF < 500
19
• Bio-based platformmolecule: Furfural
> Available: annual global production 25.104 tons
> Produced by sugarsdehydration
> Obtained from agriculture co-products rich in pentosans: corncobs, bagasse…
> Platform for the production of furan, piperidine, furfurylalcohol…
• Epoxy resin pre-polymerscleaning
> Specifications
OO
Property Specification
Technical performanceMelting point < 0°CBoiling point 100°C <...< 250°C
SolubilityHansen parameters TGPA δD=17,4 , δP=6,1, δH=6,4
radius: 12,38Safety
Flash point > 61°Clog Kow < 3
EnvironmentVapour pressure < 10Pa, 20°CBioaccumulation BCF < 500
Rd RED= d/R
RED < 1 soluble
RED > 1 insoluble
Hansen solubility parameters (δD, δP, δH)
BADGE TGPA
20
Predictive methodology
O
OH
OOO
O
OO
O
OO
O
N
Allyl furoate
Amyl furoate
Furfuryl alcohol Furyl butyl imine
2-MeTHF
Pool of derived molecules
21
Predictive methodology
O
OH
OOO
O
OO
O
OO
O
N
Allyl furoate
Amyl furoate
Furfuryl alcohol Furyl butyl imine
2-MeTHF
Pool of derived moleculesProperties prediction
Comparison withspecifications
Molecule Melting Point [°C] Boiling Point [°C] Flash Point [°C] Vapor Pressure(@293.15K) [Pa] BCF Log(Kow) RED TGPA
Allyl furoate 3 200 59 26 4 1,6 0,2Amyl furoate 0 236 88 4 39 2,7 0,1
2-MeTHF -81 77 -12 12839 2 1,2 0,2Furfuryl Alcohol -15 163 69 59 0 0,4 1Furyl butyl imine 109 201 35 3 2 2,9 0,5
Specifications < 0 100<…<250 >61 <10 <500 <3 <1
22
Predictive methodology
O
OH
OOO
O
OO
O
OO
Selection of one candidate
of interest
OO
O
O
N
Allyl furoate
Amyl furoate
Furfuryl alcohol Furyl butyl imine
2-MeTHF
Pool of derived moleculesProperties prediction
Comparison withspecifications
Molecule Melting Point [°C] Boiling Point [°C] Flash Point [°C] Vapor Pressure(@293.15K) [Pa] BCF Log(Kow) RED TGPA
Allyl furoate 3 200 59 26 4 1,6 0,2Amyl furoate 0 236 88 4 39 2,7 0,1
2-MeTHF -81 77 -12 12839 2 1,2 0,2Furfuryl Alcohol -15 163 69 59 0 0,4 1Furyl butyl imine 109 201 35 3 2 2,9 0,5
Specifications < 0 100<…<250 >61 <10 <500 <3 <1
23
Predictive methodology
O
OH
OOO
O
OO
O
OO O
O
O
O
N
Allyl furoate
Amyl furoate
Furfuryl alcohol Furyl butyl imine
2-MeTHF
Pool of derived moleculesProperties prediction
Comparison withspecifications
Tests within the targeted
application
Selection of one candidate
of interest
24
Reverse design
OO
Specifications
25
Reverse design
OO
Specifications
Virtual laboratory
Candidates molecules
Specificationsmatching
IBSS
OO
CH3
CH3
O
O
O
O
O
O
O
O
O
CH3
26
Reverse design
OO
Specifications
Virtual laboratory Real laboratory
Candidates molecules
OO
CH3
CH3
O
O
O
O
O
O
O
O
O
CH3
Specificationsmatching
Selection of the best candidate (syntheticroute and expected
properties)
IBSSRetrosynthetic analysis :Best synthetic routes to respect economies of atoms, energy and reaction steps
27
CH2
O
OO
R
OO
R
OHO
+O
R
O
+ H2O
B-
H+
OH R
R
Cat NaOH, 50°C, 2hyield : 90%
Aldolisation/crotonisation
O
O
Br + P OEt
EtO
EtO
P OEt
EtO
EtOOC O
P OEt
EtO
EtOOC O
OO
+O
O
O
a)
b)
150 °C
70 °C
B-
Arbuzov and Wittig Horner reactions
Yield 90%
Yield 41%
?
Reverse design
OO
Specifications
Virtual laboratory Real laboratory
OO
CH3
CH3
Candidates molecules
Molecule Melting Point [°C] Boiling Point [°C] Flash Point [°C] Vapor Pressure(@293.15K) [Pa] BCF Log(Kow) REDTGPA
6 223 91 12 2 2,3 0,1
Specifications < 0 100<…<250 >61 <10 <500 <3 <1
OO
CH3
CH3
OO
CH3
CH3
O
O
O
O
O
O
O
O
O
CH3
Specificationsmatching
Selection of the best candidate (syntheticroute and expected
properties)
Tests within the targeted
application
IBSS
Aldolisation/crotonisationvs Wittig-Horner reaction
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Predictive
• Synthesis abiding by principles of green chemistry: oxydative esterification withTBHP/KI, one step from furfural (yield 90%)
• Matching specifications
• Solubility of epoxy resin pre-polymer reached (100g/L)
• 100% bio-based product (amylalcohol)
• Green synthesis : aldolisation-crotonisation with3-methylbutan-2-one, one step from furfural (yield 90%)
• Matching specifications
• Solubility of epoxy resinpre-polymer reached (100g/L)
• Generated by CAMD tool in 3 minutes
Reverse design
OO
CH3
CH3
OO
O
29
Conclusion
Searching for green solvents meets specific industrial needs
New methodologies are essential to be rational and efficient
Reverse design is proved to be a performing methodology
� To generate bio-based molecules
� In agreement with specifications
� Time and cost savings
� Integration of environmental parameters
Opportunity to switch towards eco-friendly processes and products
> Current work on an european project ECOBIOFOR to develop novel bio-based solvents to be used in the Coatings Industry (via easier/greenerchemical or biotech- transformation ways)
30
IBSS
Acknowledgements
• Agromolecules Reactivity team of the Laboratoire de Chimie Agro-industrielle
• Laboratoire de Génie chimique
• French national research agency
• European Union (FP7)ECOBIOFOR has received funding from the European Union Seventh Framework Programme(FP7/2007-2013) under Grant Agreement nº [605215].
31
LCA : Two sites in South France
• INP-ENSIACET3400 m2
R&D
• INP-ENIT1335 m2
Demonstration
Toulouse Tarbes
Analysis
Fractionation Chemical reactivity(lipochemistry)
ProcessesMecanisms & modeling
Biomass
• Agriculture• Agro-industry• Forest• Microalgae• Animal residues• …
Bioproducts
• Agromaterials• Surfactants• Additives• Solvents• Lubricants• Aromas• Adhesives• Pigments• …
Life Cycle Sustainability AssessmentEnvironmental LCA ; Life Cycle Costing ; Social LCA
Pilot units : extraction
Pilot units : chemical reaction
Pilot units : extrusion
Pilot units : separation
Analytical (5 rooms ) + Syntheses (4 rooms )
Liquid chromatography: HPLC, HPLC semi-preparative, HPLC-MS, PCSI, HPTLC, TLC-FID, SEC
Gas chromatography: GC-FID, ATD-GC-MS, ATD-GC-MSn/FID, GC-MS, GC-Sniffing.
Spectroscopy: FTIR/UV, NIR, NIR on-line & FTIR on-line, NMR 300 MHz (1H, 13C, 2D). 3D Raman
Physico-chemical analysis
Micro-sensors and micro-laboratories
Sensory analysis
…
AGROMAT : Platform (1200 m 2) for industrialdemonstration (1 ton/h) for agromaterials
M. Le Ministre Michel Barnier
