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GREEN CHEMISTRY Concetto di Bioraffineria Dr. Luca Forti Laboratorio di Biocatalisi Dipartimento di Chimica Università degli studi di Modena e Reggio Emilia.

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Presentazione sul tema: "GREEN CHEMISTRY Concetto di Bioraffineria Dr. Luca Forti Laboratorio di Biocatalisi Dipartimento di Chimica Università degli studi di Modena e Reggio Emilia."— Transcript della presentazione:

1 GREEN CHEMISTRY Concetto di Bioraffineria Dr. Luca Forti Laboratorio di Biocatalisi Dipartimento di Chimica Università degli studi di Modena e Reggio Emilia Facoltà di Bioscienze e Biotecnologie

2 7. Use of renewable feedstocks A raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable

3 Petroleum feedstock Fuels Solvent Bulk chemicals Plastics Fibres Fine chemicals Oils Petroleum refinery Present situation: organic industrial production from

4 Organic feedstocks for the chemical industry Oil Natural gas Carbon Biomass Ethylene Propylene Butadiene Benzene Toluene Xilenes Syngas Methanol Hydrogen Anthracene Nafthalene Fossil resources Natural polymers (cellulose, rubber) Fine chemicals Emerging feedstocks for the chemical industry

5 The challenge Organic industrial production from renewable resources (biomass)

6 Chemical from renewable resources Advantages 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

7 Chemical from renewable resources Advantages Extend the lifetime of available crude oil supplies Mitigate the build up of greenhouse CO 2 in the atmosphere Feedstock is flexible, non-toxic, sustainable Feedstock supplies are domestic Products usually biodegradable

8 Crude oil Natural gas Coal Oil refinery Bio refinery Consumer Biomass Carbohydrate CO 2 > 10 6 years

9 Chemical from renewable resources Disadvantages 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 processes are needed for each feedstock

10 Fuels Solvent Bulk chemicals Plastics Fibres Fine chemicals Oils Grain Bio-refinery

11 Risorse rinnovabili Materiali biologici grezzi Biomateriali Energia Carburanti Biochimici Oli ed inchiostri Coloranti e pigmenti Vernici Detergenti Adesivi Biopolimeri Materiali compositi Solidi: carbone, lignina, bagassa Liquidi: etanolo, metanolo, olio combustibile Gassosi: syngas, metano, idrogeno Additivi ossigenati per carburanti Fenoli e furfurale Acido acetico Acidi grassi Tensioattivi Prodotti per agricoltura Prodotti chimici speciali Alimenti Mangimi Intermedi farmaceutici

12 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.

13 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 allinterno del processo con cui si origina in modo tale da adattarsi ai successivi processi di trasformazione per ottenere un prodotto target.

14 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.

15 Materie prime materiale biologico grezzo Processi di trasformazione Prodotti Sostanze 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.

16 Schema generale di bioraffineria

17 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

18 LCF-Biorefinery, Phase III

19 Hydrolysis (Chemical) Hexoses Pentoses Lignin Dehydrogenation Hydrolysis Hydrogenation Crystallisation Dehydration Hydrogenation Crystallisation Hydrogenation Hydrolysis Oxidation Phenol derivatives, hydrocarbons Phenol derivatives, catechols Vanillin Furfural Polyols (Xylitol) Xylose Hydroxymethylfurfural Levulinic acid Polyols Glucose

20 Levulinic acid furfural 5-aminolevulinic acid 5-(hydroxymethyl)-furfural

21 USI UNITA C5/C6 Meterie prime rinnovabili (fonti di carboidrati e lignina lignina Glucosio da cellulosa e amido Ac. 3-chetoadipico Ac. 2-chetoglutaricoAc. glutammico Ac. 3-chetoadipico 1,2,5-pentantriolo Ac. glutarico Nuovi poliesteri Nylon Polimeri Nylon 4

22 whole-crop biorefinery

23 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, bran Germ oil Gluten Steepwater Latex copolymers Fermentation feedstocks Pharma & cosmetic aids Surfactants Polyols

24 Green biorefinery

25 biomass Hydrolysis Hexoses Pentoses fermentation Ethylene Ethanol Ethylene glycol Acetaldehyde Acetic acid Acetone Butadiene Acrylic acid Glycerol Propane Propylene butanol Butanediol Propanediols Lactic acid Succinic acid Butyric acid

26 Ethanol fermentation

27 ECONOMIA DELLETANOLO (C2) CH 2 =CH 2 CH 3 CH 2 OH CH 3 CHO CH 3 COOH Etil benzene Etil bromuro Etil cloruro Etilen cloridrina Etilendiammina Etilen dibromuro Etilen dicloruro Etilen glicole Etilenimmina Etilen ossido Dietil chetone Dietilen glicole Vinil acetato Polimeri Acido acetico Anidride acetica Prodotti aldolici Butil acetato Butil alcol Butirraldeide Cloralio Etilenimmina Piridine Acetammide Acetanilide Acetil cloruro Anidride acetica Dimetil acetammide Acetati di cellulosa Esteri

28 Commodity chemicals from ethanol Some organic commodity chemicals from fermentation ethanol in Brazil

29 Lactic acid is produced by fermentation from sucrose or fructose Products: Ethyl lactate: Biodegradable solvents chiral building block L-lactic acid:acrylic acid biodegradable polymers emulsifiers Lactic acid

30 Polylactic acid Polylactic acid (PLA) is not a new polymer, it has been known since 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. J. Lunt, Polymer Degradation and Stability, 59, (1998), Lactic acid Low MW PLA Lactide High MW PLA Polymerisation Depolymerisation Catalytic polymerisation Separation by continuous distillation

31 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

32 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

33 FROM BIOMASS TO CHEMICALS THROUGH Physical methods Thermal methods Chemical methods Microbial methods

34 Physical methods They separate and isolate the different components of biomass leaving unmodified their structure examples the production of: Polysaccharides (cellulose, starch, agar alginate…) Disaccharides (lactose, sucrose) Triglycerides Natural rubber Flavour and fragrances, farmaceutical

35 Simple extraction of materials Biomass Extraction Purification Usage Palm oil press

36 Pyrolisis Production of Bio-crude Decomposition at temperature between °C in absence or with low amount of oxygen to produce liquid organic fractions similar those ones obtained from petroleum Thermal Conversions

37 Gasification Production of Bio-gas Controlled combustion around 1000°C to produce synthesis gas

38 The syngas economy Current (fossil fuel) process CH 4 + H 2 O CO + 3H 2 Nickel oxide catalyst, 300 °C, 30 atm CO + 2H 2 CH 3 OH CO 2 + 3H 2 CH 3 OH + H 2 O Cu and Zn catalyst, 300 °C, 100 atm Gas from biomass

39

40 Methanol economy MeOH Biomass + H 2 O Fisher-Tropsch Gasoline N 2 NH 3 H 2 O / Rh/Se/TiO 2 EtOH -H 2 O CH 2 CH 2 Polymers Oligomers Syngas aldehydes acids alcohols CO / Ir/Ru CH 3 CO 2 H CO 2 H CO 2 Urea HCHO Plastics Esters Ethers Alkanes HZSM-5 O O 2 / Ag Surfactants Aromatics Pt / alumina CO, H 2 Alcohols HCl MeCl Polymers Paints Adhesives CO + H 2

41 Chemical conversion

42 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

43 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

44 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

45 Industrial use of fatty acid Seed crushing and separation High temperature hydrolysis Distillation CrystallizationSupercritical 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

46 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.

47 Microbial conversion Dear God: I pray on bended knees, That all my syntheses, Will never be inferior, To those conducted by bacteria Organic Chemists Prayer (unknown origin)

48 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

49 Fermentations Carbohydrates Plant-oils Methanol Natural carbon sources are used for production of biomass and for de novo synthesis of products Some classical fermentation products… R-COOH acids R-OH alcohols Vit. B 12 vitamins NH 2 -CR-COOH aminoacids … and some not so common products Hexanoic acid Bioplastics Catechol

50 Biotransformation reactions Carbohydrates Plant-oils Methanol 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 Biotransformation processes can be used for production of numerous fine and specialty chemicals

51 Polyhydroxyalkanoates (PHAs) Biodegradation to CO 2 and H 2 O Sunlight Crop Sugar solution Fermentation PHAPlastic product

52 Sunlight Basata sulla Modifica del metabolismo di alghe (rinnovabile e privo di inquinamento) H2H2 Produzione di bio-idrogeno luce solare + alghe + acqua H 2 Idrogeno + celle a combustibile o generatore a turbina = elettricità

53 Draths-Frost biotechnological synthesis Typical feed solution: In 1 litre of water6 g Na 2 HPO g MgSO 4 10 g bacto tryptone3 g KH 2 PO 4 1 mg thiamine 5 g bacto yeast1 g NH 4 Cl 10.5 g NaCl10 g glucose (62 mmol) Yield = 20.4 mmol % Yield = 33 %

54 Growing biomass Land usage: CAP (Common Agricultural Policy) Fertilisers Pesticides/Herbicides Transportation/Infrastructure Reduced CO 2 ???

55 THE FUTURE CHEMICAL INDUSTRY ? Past Present Future


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