“Green Chemistry in Italy”Prof. A. CitterioDipartimento CMIC

Via Mancinelli 7 - Milano

Prof. A. Citterio

Summary

• Introduction to green chemistry in Italy

• The actors

• Biomass Supply and Availability

• Some case study in BioGreen Chemistry

• Some case study in Green Chemistry

• Focus on perspectives

• Conclusion

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Prof. A. Citterio

Global

Carbon Footprint

State of the World 2013:

Is Sustainability Still Possible?

ISBN: 978-1-61091-449-9Italy

Prof. A. Citterio

Advantages of Changing Feedstock

• Waste is a disposal problem • Growth from increasing production volume

• Waste is a feedstock opportunity

• Growth from increasing added value

Fossil Carbon Economy -carbon is used and discarded

Bioproducts Economy -carbon is recycled

Carbon cycle in Nature

Carbon cycle in Industry

Fossil carbon

Renewable Carbon cycle in

Nature

Carbon cycle in Industry

Prof. A. Citterio

Why Green Chemistry in Italy?

• A more careful attention to sustainability will help in defining more competitive products with appropriate design and economics

• Traditional chemistry (with its light and shade) is in crisis and will not recover easily if not appropriately supported.

• This poses new opportunities in the apparently more sustainable area of biobased products

• Bioeconomy is mainly declined as biorefinery (energy context) by using renewable resources from agricultural or forestry origin avoiding competition with food and can make available on the market new product with a better life-cycle.

• The resulting availability of domestic raw materials will decrease the import and will contribute to reduce the relevant debt of this nation, helping in meantime the reconversion to production of big non-competitive sites

• EU policy orient the sector and will help the private investment, recovering the inventing ability of Italian peoples.

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Prof. A. Citterio

Example of Bio

National Networks:

• Other clusters

• Smart communities

• Energy

Regional clusters

Corporate - Institutional Initiative

• ENEL

� ENI - Green chemistry project in Porto Torres,

� Banks (Cariplo, S, Paolo, ..

� Italy Clean Tech

University

• Velica Project

• Ager Project

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• Eco-industrial parks

• Environmental parks

• Local Incubators

• Spin off

• Galatea bio. Tech.

• Start up

• Bioecopest

New SMI Initiatives

• Frumat

• Carmen Hock-Heil

• Le Calorie

Prof. A. Citterio

Bio-Green Initiatives

• Cluster Tecnologico Nazionale della “Chimica Verde”

SPRING – Sustainable Processes and Resources for Innovation and National Growth

(Biochemtex (Tortona), Novamont (Novara) e Versalis (San Donato))

Targets:

• Renewable resources as raw materials

• Bio-refineries

• Bio-based Products

• Support framework to R&D activities

• Regional Clusters (i.e.

• Lombardy Green Chemistry Association LGCA )

(Consorzio Italbiotec Innovhub, Stazioni Sperimentali per l’industria

SSI, Politecnico di Milano, Università degli studi di Milano

• Bioeconomy development

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Prof. A. Citterio

Approaches to the Use of Renewable Raw

Materials

• Duplication of products and structures: biomass used to prepare known petrochemical derivatives … with relative facility, but limited economic

• Duplication of properties: biomass is used to duplicate interesting service properties … with relative difficulty, but of wider economical opportunity

• Development of new eco-compatible products.

Sustainable Raw Material

New

process

Substitution of conventional

product

Sustainable Raw Material

Conventional process

Alternative product

Sustainable Raw Material

New

process

Alternative product

Prof. A. Citterio

Biomass Supply and Availability9

Biomass waste streams

digesting, burning, fodder, landfill

Biological degradable fraction ofindustrial and household waste

≈ 9.2 million tons/year

Main treatment: composting,

Other biomass streams(No waste status)

Vegetal products from agricultureand forestry, animal manure,

energy crops...

≈ 4.4 million tons/year

Main treatment: composting,digesting, burning, fodder, biofuels

Primaryby-products

Secondaryby-products

Tertiaryby-products

Prof. A. Citterio

Processing to Bio-products10

Energy & Heat

Bulk Chemical and Fuels

Bioplastics &

Biopolymers

Food &

Feeds

Pharma &

Cosmetics

Prof. A. Citterio

Main Biomass Feeding Constituents

Starch: 70-75% (wheat)

� Rapidly available and hydrolysable

� Basis for actual “biorefineries”

Oils: 4-7% (wheat), 18-20% (soy)

� Rapidly separable from plant

� Basis for oleochemistry and for biodiesel

Proteins: 20-25% (weat), 80% (soy)

� Key components of foods

� Applications in chemical products

O

HO

OOH

OHO

HO

O

OH

OH

O

HO

OOH

OHO

HO

O

OH

OH

O

HO

OOH

OHO

HO

O

OH

OH

O

HO

OOH

OH

O

O

O

O

O

O

( )7

( ) 7

( ) 7

NH

HN

NH

HN

NH

HN

NH

HN

NH

OH

O

S

O

O

N

NH

O

OH

O

NH2

O

O

OH

O

HN

O

NH

O

Prof. A. Citterio

Main Biomass non Feeding Components

Lignin : 15-25%� Complex network of aromatics� High energy content� Resists biochemical conversion

Emicellulose : 23-32%� Xylose is the 2nd most abundant

sugar in biosphere� A collection of 5- and 6-carbon

sugars linked together in long, substituted chains- branched, marginal biochemical feed

Cellulose : 38-50%� Most abundant carbon form in

biosphere� Long polymer chains of beta-linked

glucose, good biochemical feedstock

Prof. A. Citterio

Betarenewables

Bioethanol Plant in Crescentino (VI)13

C6H6O6 →→→→ 2 CH3CH2OH + 2 CO2

51% 49%

25.4 kg

8.14 kg

CO2

8.16 kg

C2H5OH

+

8.16 kg

Lignin/O

+40.000 ton

Prof. A. Citterio

ADIPIC ACID (ADA)14

2.3 million tons growth at 3-5% /year

Demand estimated (2012)

Nylon 66 (85%)

Polyurethanes (5%)

Adipic esters (4%)

Others (6%)

START –UP FirmsBIOAMBER (US)CELEXION (US)GENOMATICADUTCH DSM

RENNOVIA (US)

VERDEZYNE (US)

Production by

BIO-BASED ROUTES

• Less expensive in the long term;

• Possible government incentives for ‘sustainable’ production

• Technology-specific market demand

UPCOMING

BIO-PRODUCERS

LICENSING DEAL

Prof. A. Citterio

Two Main Patented Alternatives15

Verdezyne process vs. Rennovia process

Glucose feedstock cost: $300/t

Cyclohexane cost (2012): $1250/t

Vegetable oils,

paraffins and

sugars

Adipic acid

Single-step fermentation by

Engineering Yeast

(C.Tropicalis, S. Cervisiae

(host)

D-glucose

Glucaric acid Adipic acid

Air oxidation

Hydrodeox.

Cost competitive with

conventional process when crude oil price is

$50 per barrel

High PotentialPotential

Prof. A. Citterio

CLUSTER GREEN CHEMISTRY - Lidia Project

Dicarboxylic Acids from Hydrolyzed Biomasses16

E. coli E. coli

D-glucose 3-dehydroshichimic acidadipic acid

cis,cis-muconic acid

succinic acid

terephthalic acid

acido furan-2,5-dicarbossilico Aldaric acid ??

Prof. A. Citterio

Best atom economy between alternative approaches:

Synthesis of Serinol from Glycerol and

Related Polyesters/amide Preparation17

NH3, H2/Pd

H2/Pd

NH3

-H2OCH3NO2+ 2 CH2O

1) NH3 2) HCl/H2O

OH-

H2/Pd

NH3

ClCH2NO2+ 2 CH2O

OH-

H2/Pd

OMeOMe

OH

O

Cl

OH

OH

OH

OH

NOH

OH

OH

O

OH

OH

NH2

OH

*Two routes:

• Chemical: NH3, Pd/C (80%)

• Biochemical - Transaminase (aminotransferase) from Pseudomonas (20%):

in situ “Glycerol → Dihydroxyacetone → Serinol”

*

polyester

polyamido-

ester

Prof. A. Citterio

Market Study High Value Compounds18

Crudeextracts

Functionalextracts

Purecompounds

• Food, feed, cosmetics

• Flavour, colour, sent, texture

• 10-75 €/kg

• Proven biological activity

• Food, food supplements (5 - 700 €/kg)

• Novel Food and Health claims

• Cosmetics (15-300 €/kg)

• Chemical Standards (20 - 400 €/mg)

• Pharmacy (... – 300 €/mg)

Nome relatore

Purification / Extraction Costs:

Comparison of Solvent Extraction with SFE19

Plant capacity(t/year)

Production cost(EUR/kg raw material)

Notes

SE SFE

300-400 3-8 4-10Medicinal plants, cosmetics,

spices

1000-1200 1-3-5 2-5food additives, specific

vegetable oils

10000-12000 0.5-1.2 0.75-1.2 coffee, hop

100000-120000 0.2-0.4 ? oilseeds

Prof. A. Citterio

Analytical Methodology for Low Abundance

Proteome

Application of ProteoMinerTM*:

� Capturing and amplifying the “low-abundance proteome” of 1) biological fluids, 2) foods and alcoholic or non-alcoholic beverages; 3) plant

� Identification of genetic diseases.

� Allergenic proteins identification in food-stuff;

� Search for biomarkers of neuropathology in cerebrospinal fluid and cancer markers in blood/urine. http://europa.eu.int/comm/research

/fp6/nest/pdf/nest_projects

Prof. A. Citterio

Natural and Industrial Ecosystems:

Industrial Metabolism

The analogy of industrial systems to natural systems:

� Both have cycles of energy and nutrients/materials.

� Strategies of nature to meet sustainability:

• recycling/decomposing

• renewing

• conservation and population control

• toxins stay in place

• multiple function of the organism

Prof. A. Citterio

Design for Environment (DfE):

Integrated Product Development

Technical

EcologicalEconomic

Raw materials Production Use End of life Raw materials Production Use End of life

Criteria

Design Measures

Change of task

Change of function

Change of working

principle

Change design

Change material

Prof. A. Citterio

Green Chemistry in Perspective

Jesper Sjöström Green Chem . 2006,8, 130-137

Green Chemistry

RESEARCH

BASIC RESEARCH

ENGINEERING

MANAGEMENT

LABORATORY PRACTICE

PRODUCTION CONSUMPTION

POLICY

POLICY

MACRO LEVELMESO LEVEL

MICRO LEVEL

Prof. A. Citterio

Inducible Defense

Inducible

� Attack plant before defenses are induced

� Trenching of leaves, stems

Prof. A. Citterio

Politecnico di Milano

Green Chemistry & Proteomic GroupDipartimento CMIC “Giulio Natta” Via Mancinelli 7, 20131 Milano

Thank You for Your Attention

Prof. A. Citterio

Bioethanol

C6H12O6 + 6O2

∆H°ch= −1612CO2+2C2H5OH+6O2

6 CO2 6 CO2

6 H2O6 H2O

C2H

5O

H C

om

bu

stio

n

∆H°ch= +119

∆H

° ch=

-2

67

2

Su

n h

ν,

∆H

° ch=

-2

83

3

Energy Diagram of ideal cycle of CO2-Glucose-EtOH.

First generation: bioethanol from starch or sugars

Second generation: bioethanol from cellulose and hemicellulose