green chemistry concetto di bioraffineria dr. luca forti laboratorio di biocatalisi dipartimento di...
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GREEN CHEMISTRYConcetto di Bioraffineria
Dr. Luca FortiLaboratorio di BiocatalisiDipartimento di Chimica
Università degli studi di Modena e Reggio Emilia
Facoltà di Bioscienze e Biotecnologie
7. Use of renewable feedstocks
A raw material or feedstock should be renewablerather than depleting whenever
technically and economically practicable
Petroleumfeedstock
Fuels
Solvent
Bulk chemicals
Plastics
Fibres
Fine chemicals
Oils
Petroleum refinery
Present situation: organic industrial production from
Organic feedstocks for the chemical industry
Oil
Natural gas
Carbon
Biomass
•Ethylene•Propylene•Butadiene•Benzene•Toluene•Xilenes
•Syngas•Methanol•Hydrogen
•Anthracene•Nafthalene
Fossil re
sou
rces
•Natural polymers (cellulose, rubber)•Fine chemicals
Emerging feedstocks for the chemical industry
The challenge
Organic industrial production from renewable resources (biomass)
Chemical from renewable resourcesAdvantages
New structural characteristics (stereochemical and enantiomerical) to be exploited in synthesis
Structural complexity of building block: reduction of reaction side products, reduction of waste material
Oxygenated building blocks: avoid the oxygenation process, which usually involve stoichiometric toxic reagents
Chemical from renewable resourcesAdvantages
Extend the lifetime of available crude oil supplies
Mitigate the build up of greenhouse CO2 in the atmosphere
Feedstock is flexible, non-toxic, sustainable
Feedstock supplies are domestic
Products usually biodegradable
Crude oilNatural gas
Coal
Oil refinery
Bio refinery
ConsumerBiomass
Carbohydrate
CO2
> 106 years
Chemical from renewable resourcesDisadvantages
Current economic circumstances (comparison with petrochemicals industry)
“Seasonal” supply
Feedstock used as source of food: questioned
Require space to grow
Wide range of materials: detrimental if new processesare needed for each feedstock
Fuels
Solvent
Bulk chemicals
Plastics
Fibres
Fine chemicals
Oils
Grain
Bio-refinery
Biomassa: materiale vegetale o animale di origine recente (nongeologica) che
puo’ essere usato per produrre diversi composti chimici e carburanti
U.S. President 1999; U.S. Congress 2000:
“The term biomass means any organic matter that is available on a renewable or recurring
basis (excluding oldgrowth timber), including dedicated energy crops and trees,
agricultural food and feed crop residues, aquatic plants, wood and wood residues, animal
wastes, and other waste materials.”
La maggior parte dei materiali biologici grezzi e’ prodotta in agricultura,
silvicoltura e sistemi microbici.
•La biomassa ha una composizione complessa, simile al petrolio.
•E’ quindi opportuna una separazione primaria nei principali gruppi di sostanze
che la compongono.
•I trattamenti successivi di queste sostanze portano alla formazione di una
“tavolozza” completa di prodotti.
•Un importante differenza col petrolio e’ che il petrolio deve essere estratto,
mentre la biomassa esiste gia’ come prodotto, principalmente in seguito a
trasformazioni agricole.
•La biomassa puo’ quindi essere modificata all’interno del processo con cui si
origina in modo tale da adattarsi ai successivi processi di trasformazione per
ottenere un prodotto target.
La bioraffineria combina le tecnologie necessarie per trasformare materiali biologici
grezzi in intermedi o in prodotti finiti di interesse industriale.
La biomassa vegetale e’ costituita principalmente da carboidrati, lignina, proteine e lipidi,
oltre a varie sostanze presenti in quantita’ minori come vitamine, coloranti, aromi e
fragranze.
Materie primemateriale biologico grezzo
Processi di trasformazione
ProdottiSostanze ed energia
•Granaglie•Biomassa ligno-cellulosica (es. Graminacee, canne, arbusti, cespugli, residui di raccolti)•Biomasse forestali (legname, sterpaglie, scarti della lavorazione del legno)•Rifiuti solidi urbani (carta/cartone, fogliame…)
•Bioprocessi (fermentazioni, bioconversioni)•Processi chimici•Processi termo-chimici•Processi termici•Processi fisici
•Carburanti (etanolo, biodiesel)•Prodotti chimici (intermedi, solventi, acidi grassi)•Materiali (polimeri, inchiostri, vernici, lubrificanti)
“bioraffineria”: un sistema simile alla raffineria del petrolio per produrre prodotti chimici,
carburanti ed energia utilizzando biomasse.
Schema generale di bioraffineria
• lignocellulose feedstock (LCF) biorefinery: uses naturally dry raw materials such as cellulose-containing biomass and wastes.
• whole-crop biorefinery:uses raw materials such as cereals or maize.
• green biorefinery:uses naturally wet biomass, such as green grass, lucerne, clover
LCF-Biorefinery, Phase III
Hydrolysis(Chemical)
Hexoses
Pentoses
Lignin
DehydrogenationHydrolysisHydrogenationCrystallisation
DehydrationHydrogenationCrystallisation
HydrogenationHydrolysisOxidation
Phenol derivatives, hydrocarbonsPhenol derivatives, catecholsVanillin
FurfuralPolyols (Xylitol)Xylose
HydroxymethylfurfuralLevulinic acidPolyolsGlucose
Levulinic acid
H2SO4 O
OH
OH
OH
OHOH
O
OHCHO
HCO2H
O
CO2HO
OOHC
H+
NH2.HCl
O
CO2H
OH
HO2COH
OH
Cellulose>200oC
200oC
+Levulinic acid
Cat / H2
1. HBr / MeOH2. NaN(CHO)2
3. HCl
DALA
Diphenolic acid
furfural
5-aminolevulinic acid
5-(hydroxymethyl)-furfural
USI UNITA’ C5/C6
Meterie prime rinnovabili
(fonti di carboidrati e lignina
O
H
HO
H
HO
H
OHH
OH
OH
ligninaGlucosio da cellulosa e amido
COOHHOOC
O
COOHHOOC
O
COOHHOOC
NH2
Ac. 3-chetoadipico
Ac. 2-chetoglutarico Ac. glutammico
Ac. 3-chetoadipicoCOOHHOOC
OH
OH
HO OH
1,2,5-pentantriolo
COOHHOOC
Ac. glutarico
Nuovi poliesteriNylon
PolimeriNylon 4
whole-crop biorefinery
Industrial uses of starch
Cereals/tubers
Starch
Modified starches•Hydrolysed•Oxidised•Esters•Ethers•Crossbondend•Dextrins
Maltodextrins
Hydrolysates
Derivatives
Paper & corrugating
Thickeners
Binders
Cobuilders
Thermoplastics
Complexing agents
Flocculating agents
Coatings
Fiber, hemicellulose, branGerm oilGluten Steepwater
Latex copolymers
Fermentation feedstocks
Pharma & cosmetic aidsSurfactants Polyols
Green biorefinery
biomass HydrolysisHexoses
Pentoses fermentation
EthyleneEthanolEthylene glycolAcetaldehydeAcetic acidAcetoneButadieneAcrylic acidGlycerolPropanePropylenebutanolButanediolPropanediolsLactic acidSuccinic acidButyric acid
Ethanol fermentation
ECONOMIA DELL’ETANOLO (C2)
CH2=CH2
CH3CH2OH
CH3CHO CH3COOH
Etil benzeneEtil bromuroEtil cloruroEtilen cloridrinaEtilendiamminaEtilen dibromuroEtilen dicloruroEtilen glicoleEtilenimminaEtilen ossidoDietil chetoneDietilen glicoleVinil acetatoPolimeri
Acido aceticoAnidride aceticaProdotti aldoliciButil acetatoButil alcolButirraldeideCloralioEtilenimminaPiridine
AcetammideAcetanilideAcetil cloruroAnidride aceticaDimetil acetammideAcetati di cellulosaEsteri
Commodity chemicals from ethanol
Product Production capacity
(109 kg/ year)
Product Production capacity
(109 kg/ year)
Ethylene dichloride 1.011 Acrylonitrile 0.078
LD polyethylene 0.663 Ethyl acetate 0.060
Ethyl benzene 0.497 Ethylene glycol 0.030
Vinyl chloride 0.461 Acetic anhydride 0.026
HD polyethylene 0.397 Monochloroacetic acid 0.024
Acetic acid 0.182 Diethanolamine 0.012
Ethylene oxide 0.163 Triethanolamine 0.012
Diethylene glycol 0.147 Chloromethane 0.007
Monoethylene glycol 0.147 Pentaerithritol 0.007
Triethylene glycol 0.147 Chloral 0.004
Acetaldehyde 0.146 Acetylsalicylic acid 0.003
Polyvinylacetate 0.143 Acetophenone 0.002
Ethylene 0.132 Ethyl ether 0.002
Monoethanolamine 0.122 Ethyl chloride 0.001
Vinyl acetate 0.080
Some organic commodity chemicals from fermentation ethanol in Brazil
• Lactic acid is produced by fermentation from sucrose or fructose
Products:• Ethyl lactate: Biodegradable solvents
chiral building block
• L-lactic acid: acrylic acidbiodegradable polymersemulsifiers
Lactic acid
Polylactic acid
• Polylactic acid (PLA) is not a new polymer, it has been known since 1932.
• Producing low molecular weight PLA is a simple process, however, making high molecular weight PLA is a more complicated affair.
• Cargill-Dow has developed a novel process involving selective depolymerisation of low molecular weight PLA to a cyclic intermediate (lactide), which is purified by distillation.
• Catalytic ring opening of the lactide results in continuous controlled weight PLA preparation.
OHCH3H
OHO
H2OO
O
O
CH3
CH3
O
*O
*H CH3
O
n
Lactic acid Lactide poly(3,6-dimethyl-1,4-dioxan-2,5-dione)
J. Lunt, Polymer Degradation and Stability, 59, (1998), 145-152http://www.cargilldow.com/home.asp
Lactic acid
Low MW PLA
Lactide
High MW PLA
Polymerisation
Depolymerisation
Catalytic polymerisation
Separation by continuous distillation
Properties and uses of Polylactic acid (PLA)
• The PLA materials have mechanical properties that lie somewhere in between that of polystyrene and PET.
• Packaging– Films– Packaging foam– Containers (biodegradable)– Coatings for papers and boards
• Fibres– Clothing– Carpet tiles (Interface Inc.)– Nappies
• Bottles– Biodegradable bottles
http://www.cargilldow.com
Vinacce
Trattamento enzimatico
Recupero estratto grezzo
fenoli
Formulazione di cibi fortificati
Purificazione e isolamento dei fenoli
Trasformazioni chimiche ed enzimatiche
Refluo defenolato
Biotrasformazione
Biomasse proteiche
Formulazione di mangimi animali
Chimica Fine
Separazione solido sospeso Solido sospeso
Concentrazione a membrana concentrato
Acqua riciclata
Methanol economy
MeOH
Biomass + H 2O
Fisher-Tropsch GasolineN 2
NH 3
H 2O / R h/S e/TiO 2
EtO H
-H 2OC H 2C H 2
Polymers
Oligomers
Syngas
aldehydesacidsalcohols
C O / Ir/R u C H 3C O 2H
C O 2H
C O 2
UreaH C H O
Plastics
EstersEthers
AlkanesHZSM-5
O
O 2 / Ag
Surfactants
Aromatics
Pt / aluminaC O, H 2
Alcohols
HCl
Me Cl
PolymersPaintsAdhesives
CO + H2
Chemical conversion
One step chemical modification
One step chemical modifications of components separated by physical methods
Examples
• Cellulose and starch derivatives• Glucose and fructose• Glycerol• Fatty acids
Two or more steps chemical modification
Examples
• Ethylene from ethanol• Sorbitol and mannitol by hydrogenation of glucose and fructose• Vitamin C in several steps from glucose• Fatty alcohols and amines from triglycerides• Alkyl polyglucoside from glucose and fatty alcohol
Industrial uses of sucrose
Sugar cane/sugar beet
sucrose
Sucrose derivative•Esters•Ethers•Acetals
Glucose + fructose
Fermentation feedstocks
Beet pulp
Bagasse
Molasses
Polycondensate (starter)
Building units (pharma)
Surfactants
Furan resins
Industrial use of fatty acid
Seed crushing and separation
High temperature hydrolysis
Distillation
Crystallization Supercritical extraction
Fractional distillationSolvent extraction
Glycerol
oil
Crude acid mix
Surfactants in alternative to alkylbenzene sulphonates
Lubricants in alternative to mineral oils
Solvents in alternative to chlorinated solvents
Fatty acids
Biodiesel
• Short chain alcohol usually employed - methanol most common (NaOH soluble in MeOH)
• Catalyst used to improve yield (system loading 1 % w/w):
– Basic catalyst most commonly used (e.g. sodium hydroxide) - lower ratio of glyceride to alcohol required (6:1). Supported guanidines have also been used successfully
– Acidic catalyst can be used as well but higher ratio of glyceride to alcohol required (30:1) - however, system is water tolerant; wet substrate can be used
– Enzyme catalysts have also been used - require lower reaction temperatures.
Oil Alcohol andcatalyst
alcohol
steam
condensate
glycerine
esters
acid
CH2
CH
CH2
COOR'
COOR''
COOR'''
+ 3 ROH
R COOR'
R COOR''
R COOR'''
+Catalyst
CH2
CH
CH2
OH
OH
OH
Glyceride Alcohol Esters Glycerol
Microbial conversion
Dear God:I pray on bended knee’s,That all my syntheses,Will never be inferior,To those conducted by bacteria
Organic Chemists Prayer (unknown origin)
• Fermentations• Biotransformation reactions
Biocatalysis and genetic engineering of microbial
metabolism provide a new approach for the generation of
building block for chemical synthesis and for the production
of consumer goods
Fermentations
COOH
CarbohydratesPlant-oilsMethanol
Natural carbon sources are used for production of biomass and for de novo synthesis of products
Some classical fermentation products…
R-COOHacids
R-OHalcohols
Vit. B12
vitaminsNH2-CR-COOH
aminoacids
… and some not so common products
Hexanoic acid
O O
CH3 HO
*n
Bioplastics
OH
OH
Catechol
Biotransformation reactions
CarbohydratesPlant-oilsMethanol
Natural carbon sources are used for the production of the biocatalyst and for the subsequent transformation of the reaction precursor into the desired product
Precursor molecules
OHO OH
N
NHO
COOH
OH
OH
NH2
OCOOH
Cl
Biotransformation processes can be used for production of numerous fine and specialty chemicals
Polyhydroxyalkanoates (PHA’s)
Biodegradation to COBiodegradation to CO2 2 and Hand H22OO
Sunlight Crop Sugar solution
Fermentation
O O
CH3 HO
*n
PHAPlastic product
Sunlight
Basata sulla Modifica del metabolismo di alghe(rinnovabile e privo di inquinamento)
H2
Produzione di bio-idrogeno
luce solare + alghe + acqua H2
Idrogeno + celle a combustibile o generatore a turbina = elettricità
Draths-Frost biotechnological synthesisO OH
+
HO2CCO2H
O
OH
OH
OH
OH
OHOH
OH
O
CO2H
HO2C
CO2HE. coli E. coli
Pt, H2
50 psi
benzene cyclohexane cyclohexanone cyclohexanol
D-glucose 3-dehydroshikimate cis,cis-muconic acid
adipic acid
Ni-Al2O3
370-800 psi
Co-O2
120-140 psiHNO3
Typical feed solution:
In 1 litre of water 6 g Na2HPO4 0.12 g MgSO4
10 g bacto tryptone 3 g KH2PO4 1 mg thiamine
5 g bacto yeast 1 g NH4Cl
10.5 g NaCl 10 g glucose (62 mmol)
Yield = 20.4 mmol% Yield = 33 %
Growing biomass
• Land usage: CAP (Common Agricultural Policy)• Fertilisers• Pesticides/Herbicides• Transportation/Infrastructure• Reduced CO2???
THE FUTURE CHEMICAL INDUSTRY
??
Past Present
Future