Masamitsu Funaoka. From Forest To Chemical Industry. Functionality Control of Phytomaterials Graduate School of Bioresources Mie University JAPAN

Size: px

Start display at page:

Download "Masamitsu Funaoka. From Forest To Chemical Industry. Functionality Control of Phytomaterials Graduate School of Bioresources Mie University JAPAN"

Tyrone Stevens
6 years ago
Views:

1 From Forest To Chemical Industry July 13, 2007 Masamitsu Funaoka Functionality Control of Phytomaterials Graduate School of Bioresources Mie University JAPAN

2 Sustainable Resources Lignocellulosics

3 Forest Carbon Flow System Switching Function n the ground Under the ground Phase II High potential Multi function Potential energy Phase I 育成 Photosynthesis Phase II 保全 Phase II 複合系利用 Phase III Successive flow in molecular level Low potential Single function C2 Time

4 Forest Carbon Flow System Switching Function Present carbon flow loop Molecular level potential Phase II Phase II plus Potential as post-petroleum Potential energy Phase I 育成 Photosynthesis Phase II 保全 Phase II 複合系利用 Phase III Conservation Wood utilization C2 Time

5 Forest Carbon Flow System Switching Function Cascade-type material flow in molecular level Phase II Phase II plus High potential Multi function Potential energy Phase I 育成 Photosynthesis Phase II 保全 Phase II 複合系利用 Phase III Petroleum level potential Conservation Wood utilization Low potential Single function C2 Time

6 Lignin C H2 H3C 3 3 H2 H2 3 H3C H2 3 H2 H3C H H2 H3C HH2C C H2 3 H3C H H2 H3C H2 3 H3C 3 2 H 3 H2 H2 3 3 C H2 H3C 3 H2 H H3C H3C HH2C HH2C C 3 2H H3C H2 3 C 2H C H2 H3C 3 H2C 2 3 H3C H H H H H H H H H H n H H H H H n H H H 3C H H H Cellulose Hemicellulose Interpenetrating polymer network Interpenetrating polymer network Model of Cell Wall Model of Cell Wall

7 Forest Carbon Flow System Switching Function Potential energy Phase I 育成 Photosynthesis Conservation Phase II Phase II 保全 Phase II plus Wood utilization Phase II 複合系利用 Cascade-type material flow in molecular level Phase III Carbohydrates Short term 1 st Breakthrough technology Refining 2 nd Breakthrough technology Functionality control Lignin Long term C2 Time

8 Forest Carbon Flow System Switching Function Present Phase III Activity Phase II Phase II plus nly carbohydrate utilization Potential energy Phase I 育成 Photosynthesis Phase II 保全 Phase II 複合系利用 Phase III Conservation Wood utilization Carbohydrates Short term Lignin Long term C2 Time

9 Biochemicals Japan USA Bio-alcohols (Poly)lactic acid Bio-polyesters [p(3hb)] 1,4 diacids (succinic, fumaric and malic) 2,5 furan dicarboxylic acid 3 hydroxy propionic acid Aspartic acid Glucaric acid Glutamic acid itaconic acid Levulinic acid 3-hydroxybutyrolactone Glycerol Sorbitol Xylitol/arabinitol

10 Switching Function Key Activity Lignin Phase II Phase II plus Successive Functionality control Potential energy Phase I 育成 Photosynthesis Conservation Phase II 保全 Wood utilization Phase II 複合系利用 Phase III Carbohydrates Short term Lignin Long term C2 Time

11 Key Material Lignin

12 Formation Mechanism and Structural Key Points

13 C2 C2 C2 Glucose -(H)4-2H Formation of precursors Formation Route of precursors Switching Function 1st key point (Methoxyl group) H H Shikimic acid Blocking of phenolic hydroxyl groups H Cinnamic acid NH 2 C C H 2 H Phenylalanine Basic C9 unit N Guaiacyl unit Monophenol Syringyl unit H H H H 3 C H 3 C H H Ferulic acid Sinapic acid Monophenol H H 3 C H 3 C C H C H C H C H C H C H C H C H C H C H Activation Deactivation Activation Deactivation Diphenol H 3 C H H H 3 C Diphenol H 3 C Coniferyl alcohol C H C H C H C H 2 H Sinapyl alcohol 2 H

14 2nd key point Formation of linear type subunits Route Switching Function Precursor Coniferyl alcohol H α β γ H Cβ Alkyl Cβ Aryl Cβ Aryl Cβ=Cα 3 Monomer H - H. H H H C5 Alkyl C5 Aryl C5 Aryl Alkyl Aryl 3 * Polymer 3 H 3 Random coupling 3 * * 3 Linear type Reactive prepolymers

15 3rd key point Nucleophiles Formation of Network type chains Route Switching Function Formation of reactive sites H2 Lignin units Carbohydrates (Hemicellulose) H H H 3 3 Network formation H H 3 3 Lignin 3 3 Network type Carbohydrates H H 3 Cα H Cα=Ο Cα Alkyl Cα Aryl Cα=Cβ α γ H β H

16 Lignin Reactive * H 3 H3C 3 Latent phenolic Latent Phenolic Polymers With Reactive Points

17 How to Utilize Reactive- and Latent Phenolic Polymers First step Design of Functional Lignin-Based Materials

18 Successive Structure Control of Lignin Lignin Latent phenolic polymers with reactive benzyl units Reactive benzyl units For creating functionality control units Latent phenolic units Cα H Cα Aryl 0.07 mol/c9 α γ H β Cβ Aryl 0.5 mol/c Cα Aryl Cβ Aryl For polymer type control From network to linear For MW control 1 mol/c9 Alkyl 3 3 For phenolic activity control

19 Functionality Control of Lignin Reactive site α β γ Cβ Alkyl Cβ Aryl Cβ Ary l --Aryl (H) 3 1. Reactive Cα Selective phenol grafting H Alkyl Cβ Alkyl Cβ Aryl Cβ Aryl --Aryl (H) 3

20 Functionality Control of Lignin Reactive site α β γ Cβ Alkyl Cβ Aryl Cβ Ary l --Aryl (H) 3 1. Reactive Cα Selective phenol grafting H Alkyl Cβ Alkyl Cβ Aryl Cβ Aryl --Aryl 2. Cα-Phenol-Cβ -Aryl Functionality control units (Switching device) (H) 3

21 How to Utilize Reactive- and Latent Phenolic Polymers Second step How to release interpenetrating polymer network within the cell wall How to achieve selective structural modifications within the cell wall

Phase-Separation System For rapid molecular separation and conversion Acid 2 nd Stage 1st Control 1 st Stage Release of IPN structure 2nd Control

22 Phase-Separation System For rapid molecular separation and conversion Acid 2 nd Stage 1st Control 1 st Stage Release of IPN structure 2nd Control For carbohydrates Hydrolysis and dissolution For Lignin Cleavage of benzyl ethers Phenol grafting 3rd Control Separation of lignin and carbohydrate

23 Hydrolysis Sugars ligomer Monomer Polymer Cellulose Phenolysis 1,1-Bis(aryl)propane type polymer 3 H n (H) Solvolysis control Solvolysis control Structure controllable C H2 H3C 3 3 H2 H2 3 H3C H2 3 H2 H3C H H2 H3C HH2C C H2 3 H3C H H2 H3C H2 3 H3C 3 2 H 3 H2 H2 3 3 C H2 H3C 3 H2 H H3C H3C HH2C HH2C C 3 2H H3C H2 3 C 2H C H2 H3C 3 H2C 2 3 H3C Lignin H H H H H H H H H H n Selective conversion control Selective conversion control

H3C H3C H2 C H3C H2 H H2 3 3 3 H2 3H 3 3 H2H2 H3C 3 H3C HH2C C H3C H2 2 H2 H3C 3 H3C H H2 3 H2 C H3C H2 H

Lignin Lignocellulosics Reaction Environment Hydrophobic solvent for ligin (Phenol derivatives) Lignin

24 H3C H3C H2 C H3C H2 H H H2 3H 3 3 H2H2 H3C 3 H3C HH2C C H3C H2 2 H2 H3C 3 H3C H H2 3 H2 C H3C H2 H H2 C 3 3 H2 H2 3 HH2C C 3 2 H3C 3 3H3C HH2C 3 H3C H2C 3 H3C 2 3 H2 3 2H 2H C 3 3 Design of Reaction System Lignin Lignocellulosics Reaction Environment Hydrophobic solvent for ligin (Phenol derivatives) Lignin (Hydrophobic) Carbohydrates Interface Carbohydrates (Hydrophilic) (Conc. Acid) Hydrophilic solvent for carbohydrates

25 1 st Stage Solvation Phase-Separation System 1st Control Release of IPN structure 2 nd Stage Aqueous layer (acid) 3rd Control 2nd Control Separation For carbohydrates Hydrolysis and dissolution For Lignin Cleavage of benzyl ethers Phenol grafting Selective structural conversion

26 Separation of lignocellulosics rganic phase Lignophenol Aqueous phase Carbohydrates

Lignophenols (% of klason lignin) Treatment time (min) Species 20 60 Yezo spruce Picea jezoensis 99.15 108.19 Japanese fir Abies firma 101.71 111.84 Slash pine Pinus elliottii 105.34 116.

27 Lignophenols (% of klason lignin) Treatment time (min) Species Yezo spruce Picea jezoensis Japanese fir Abies firma Slash pine Pinus elliottii Japanese hemlock Tsuga sieboldii Japanese cedar Cryptomeria japonica Japanese birch Betula platyphylla Japanese oak Quercus mongolica Apitong Dipterocarpus grandiflorus Kapur Dryobalanops aromatica ne step process

28 Phase-separation system Polymer Type Network type Native Lignin 2H H2 C 2 H2 H2 3 H2 C H2 H2 3 H3C 3 3 H3C 3 H3C 2H H3C H2 3 H H2 3 3 H2 3H H3C 3 3 H3C 3 3 H2H2 H3C 3 3 H2C H2 C HH2C C H2 2 H3C H2 C H3C 3 H3C HH2C 3 H C H2 3H3C H3C HH2C Building Unit R H Functionality: Reactivity controllable Structure controllable Molecular weight controllable H3C 3 H * Hybridization Linear type Polymer type: Linear-type Unit: 1,1-Bis(aryl)propane Interunit linkage: Alkyl-aryl ether Molecular weight (Mw): Softwood type Hardwood type Solid-liquid transformation: Softwood type 170 Hardwood type 130 Activity: Phenolic (latent) Lignophenol H (H) 3 n 1,1-Bis(aryl)propane type polymer

29 Conversion of Carbohydrates Mw=100,000 Phase -separation time 10 min Mw=1,000 Mw= min min Phase -separation time 60 min min min Phase- separation time 120 min Carbohydrates min min Time (min)

30 Design of Intramolecular Switching Devices For Successive Structure Control

31 Lignophenol model 3 3 H Switching unit H R H 3 3 H H 3 C H 3 C H 3 H H 3 H H 3 3 H 3 C 3 H H H H 3 C H 3 H H H3 C H H H 3 3 H 3 C H H H H 3 C H 3 H 3 H H 3 C H 3 H H

32 Functions of Switching Devices 1. Functionality control Molecular weight Phenolic activities 2. Polymer structure control

33 Switching Devices Control device Switching device Switching unit H H H R H 3 Free R 3 3 H 3 3 Etherified R H 3

34 Switching Function Free Etherified H H R 3 3 Etherified R H 3 Free H 3 Spruce Birch Total phenolic H (Wt%) riginal N NaH treated Molecular weight (Mw) Total phenolic H (Wt%) riginal N NaH treated Molecular weight (Mw)

35 Switching Function 2 次機能制御システム Switching device Control device α β (H) γ 3 Cβ Alkyl Cβ Aryl Cβ Aryl --Aryl Switching device H H 3 3 (H) H 3 (H) H 3 Switching device H H 3 H Alkyl Cβ Alkyl Cβ Aryl Cβ Aryl --Aryl FF (H) 3 H H H H H H H H H H (H) 3 N H H H H H (H) 3 H H 3 H H H H

36 Switching Function Switching Function 3000 Molecular weight Switching device Control device H 3 C H 3 H Frequency of switching device (mol/c9) Switching Device Frequency of switching device (mol/c9) Ligno-2,4-dimethylphenol Ligno-p-cresol Ligno-p-ethylphenol Ligno-p-n-propylphenol Ligno-p-iso-propylphenol H H H H H Molecular weight (Mw)

37 Switching Control Switching unit H H R 3 3 Cβ Ο Aryl linkage Switching control Nucleophilicity... Attaching electron releasing- or attracting units Mobility... Controlling the extension of switching units

38 Switching Function Function of Switching Device Controls of Nucleophilicity and Mobility H H Molecular weight (Mw) Spruce (softwood) type ,6-Dimethylphenol / Switching device H 3 3 p-n-propylphenol H 3 3 2,4-Dimethylphenol

39 Switching Function Function of Switching Device Controlled molecular weight riginal Switching treatment LC1 LC2 Mobility control H 4 H3C 2 Chain extension H 3 H3C 2 H 2 H3C 2 H 1 H 3 C 3 LC3 LC4 3 (H)

40 Functions of Switching Devices 1. Functionality control Molecular weight Phenolic activities 2. Polymer structure control

41 Switching Devices Switching unit Reactive device To network type polymers Stable device To linear type polymers * H H R H H R R

42 Network Control H H 3 (H) 3 Network type H H H H H H H H H Reactive devices H H H H (H) 3 (H) H H H H H H H H H H Controlled network Hybrid devices H H 3 3 (H) H H H H H H H H H Stable devices Linear type

43 Function of Switching Devices Terminal units H 4 H H H3C 2 H 3 2 H 2 H3C 2 1 H 3 C H Spacer units riginal lignophenol unit 3 3 (H) Detailed Network Control

44 Phase Separation System Lignocellulosics Softwood, Hardwood, Grass Woody and agricultural wastes, Waste papers Process Input ne step Two step Process I Process II Process III utput Lignophenol Carbohydrates

45 1 st System Plant in Mie University (2001)

46 2nd System Plant (2003)

47 3rd System Plant (2007)

48 Applications of Lignophenols

49 Application of Lignophenols H H Recyclable Composites R (H 3 C) 3 3 Thermoplastic Cellulose Biopolyesters Inorganic materials Glasses Metals thers H H R Raw materials for recyclable polymers 3 (H 3 C) 3 Detachable adhesives Structure controllable Switching devices for material recycling H H R 3 (H 3 C) 3 Network controllable

50 Application of Lignophenols H H R 3 Electromagnetic shielding materials (H 3 C) 3 Carbon molecular sieving membranes Carbon network H H Photoresists R 3 UV barriers (H 3 C) 3 Enzyme Supports Controlled phenolics Bioreactor, Affinity chromatography

51 Application of Lignophenols Performance control agents H H For adsorbents Proteins, Metals R (H 3 C) 3 3 Blocked Phenolics Lead-acid battery Enzymes Antioxidants Controlled phenolics H H R Solar cell 3 (H 3 C) 3 Conjugated system

52 Sustainable Industrial Network

53 Phase III Switching Function New Material Flow Phase-separation process Phase II Phase II plus Lignophenols Switching functions Phase I Phase II Phase II Potential energy 育成保全複合系利用 Carbohydrates flow Aliphatic Lignin flow Aromatic Time

54 Future Sustainable Industrial Network Forestry Wood Industry Refining Frontier Industrial system Potential Up Potential Down Cemical Industry C2 C2 C2 C2 C2 ne way loop C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2

Characterization of liquefied products from model woody components in the presence of mineral acid catalysts

Sustainable Chemistry 187 Characterization of liquefied products from model woody components in the presence of mineral acid catalysts Q. Wang 1, Q. Chen 1, P. Apaer 1, Q. Qian 1, T. Maezono 1, N. Mitsumura