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