Determination of functional groups in pulp and paper samples

Laboratory of Fibre and Cellulose Technologywww.abo.fi

Cellulose Technology

Pedro Fardim, Jan Gustafsson

Åbo Akademi

Forest Based Biorefinery

“Chemical and Engineering Challenges and Opportunities ”

• Natural polymers such as starch, cellulose, chitin, carrageenan

• Produced by plants and animals

Polysaccharides

Cellulose

Chitin

cotton

coconut

bacteries

Starch

crab corn

What is Cellulose Technology ?

Cellulose

• 50 % of biomass on earth

• 100-150 billion-ton per year

• One tree: ~14 g of cellulose per day

• Vegetal (plants)

• Seaweed (valonia, microdycon)

• Biosynthesised by bacteria (acetobacter xylonium)

Cellulose sources

Wood is the main source

Cellulose

Wood (86%)Other (14%)

softwood (51%) hardwood (35%)

Pulp&paper (80%) Dissolving pulp (20%)Regenerated celluloseCellulose derivatives

Dissolving pulp processes

• Target: remove hemicelluloses and lignin

• Chemical pulping processes:

– Bisulphite

– Sulphite-soda

– Prehydrolysis kraft

• Bleaching (TCF)

Degree of polymerization of cellulose from different raw materials

Tracheid

Macrofibril

Cell wallMicrofibril

Crystallite

0.8 nm

Cellubiose unit

Cellulose chemistry and nanostructure

Cellulose chemistry

Comprehensive Cellulose Chemistry Vol 1D. Klemm,et al. (Eds.)Wiley-VCH, Chichester, 1998

Cellulose chemistry

Supramolecular structure

Cellulose Polymorphs

• Four polymorphs identified by X-ray diffraction

• Cellulose I

• Cellulose II

• Cellulose III

• Cellulose IV

Solid state 13C-NMR

Facts about Cellulose I

• Wood, cotton, shells of certain marine animals are : cellulose Iβ

• Primitive organisms, such as bacteria: Iα cellulose

• The crystalline phases Iα and Iβ are in various proportions depending of the origin of the cellulose

• Allomorph Iβ is thermodynamically more stable than Iα.

• Transformation of the Iα phase into Iβ is irreversible.

Cellulose II

Cellulose I, native cellulose

C(3´) - O(5´)

C(2´) - C(6´)

C(6) - C(3´)

Cellulose II, regenerated cellulose

C(5) - C(3’)

C(2) - C(6’)

Cellulose II

XRD of Cellulose I and II

Facts about Cellulose I and II

• Polymorph II is energetically more stable than polymorph I. This is the reason why it is possible to convert cellulose I into cellulose II but not the contrary.

• The fibrillar arrangement of regenerated cellulose differs somewhat from the one of native cellulose, as arrangement in distinct layers does not exist.

• In the same way, the helicoidal structure, which exists in the cellular walls of native cellulose, does not exist in precipitated or regenerated cellulose fibres.

Cellulose III

• A treatment with ammonia or with certain amines as the ethylene diamine allows the preparation of cellulose III either from the cellulose I (which leads to cellulose III1) or from the cellulose II (which leads to cellulose III2).

Cellulose IV

• Cellulose III, heated at high temperatures in glycerol, is transformed into cellulose IV. There are two forms: cellulose IV1 and cellulose IV2

obtained from cellulose III1 and III2, respectively.

• Cellulose IV is a disordered form of cellulose I, which explains why it can be found in X-ray diffractions for native cellulose of some plants.

Cellulose microfibril

Fibre Ultrastructure

Kolman/Côté (1984)

Elementary fibril (2 - 5 nm)Microfibrils (10 - 30 nm)

Macrofibrils

Morphological structure

Pore structure

Surface area

Thermal properties of cellulose

Mechanical properties of cellulose

Cellulose reactivity

Cellulose activation

Cellulose reactions

Cellulose derivatives

Cellulose Based Materials

• Fibres

• Fibrills and nanorods

• Particles and beads

Cellulose Fibres

Zhang et al, Carbohydrate Polymers 59 2005, 173

Regenerated fibres (Textiles) Wood fibres (Papermaking)

From wood to polysaccharides

CelluloseWood

Hemicelluloses

Lignin

Extractives

Disassembly

nanocellulose

cellulosesolution

hemicellulosesolution

Disassembly of wood polysaccharides

Method Products

Microfluidization of pulp microfibrillar cellulose (nanocellulose)

Acid treatment of pulp Cellulose nanorods

Chemical pulping (sulfate, pre-

hydrolysis sulfate, sulfite)

Paper pulp, dissolving pulp, lignin

Organosolv pulping (ethanol,

acetic acid, others)

Paper pulp, dissolving pulp, lignin

Ionic liquids (ILs) Fractionation of wood components

Supercritical fluid extraction Extraction, gasification, biofuels

Microfibrillar cellulose (MFC)

Preparation of MFC

Pulp pre-treatment

Modification of MFCs

Some questions about MFCs

• Energy consumption in processing

• Usually produced to 2% dispersion in water

• Residual of hemicelluloses

• Surface modification/reactivity

• Balance between stabilization of dispersion/functionalisation

Cellulose nanorods (nanocrystals)

Microfibrils

Nanocrystals

+ Acid

acid (HCl, H2SO4)

concentrations ( 65%)temperature (40°C)hydrolysis time (1 – 2 h)acid-to-substrate ratio (0.1 – 0.5 mol/g)

Some questions about cellulose nanocrystals

• Low yield

• Stabilization of nanocrystal dispersions

• Functionalisation of nanocrystals

Cellulose Materials

Cellulose

Particles Sponges

Composites

New functionalfillers

Paper coating pigments

Drug releaseChemical sorbents

Biomaterials

Medical applications

Rheologymodifiers in coating, food, cosmetics Binder and co-binder

Lab. of Fibre and Cellulose Technology

Form factor

3 3,5 4 4,5 5 5,5 6

Selluloosapitoisuus, %

Beads of regenerated cellulosex100 x1000 x5000 x10000

x100 x500 x5000 x10000

100 mm 10 mm 5 mm 1 mm

Summary

• Cellulose can be modified usinghomegeneous or heterogeneous methods

• Cellulose derivatives have borad applicationareas

• Regenerated cellulose can be used as fibres, particles and sponges

• Cellulose fibrils have potential applicationsin several technological areas

Determination of functional groups in pulp and paper samples

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