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The Chemistry of Wood and Kraft Pulping

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Typical Composition of Wood


Cellulose (41-53%) Hemicellulose (25-41%) Lignin (16-33%) Extractives (2-5%) Inorganics (<1%) Nitrogen compounds (traces)

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Compositions of Several North American Pulpwood Species


Species Balsam Fir Eastern Hemlock Eastern White Cedar White Spruce Jack Pine Tamarack Typical Softwood Beech Trembling Aspen White Elm Red Maple White Birch Yellow Birch Typical Hardwood Cellulose, % 44 42 44 44 41 43 43 42 53 49 41 41 40 46 Hemicelluloses, % 27 26 25 29 30 28 28 36 31 27 35 40 39 34 Lignin, % 29 33 31 27 29 29 29 22 16 24 24 19 21 20

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Cellulose (1)
One

sugar Linear Long Reducing and nonreducing ends Partly crystalline

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Cellulose (2)

OH O O HO OH O O HO OH

OH O HO OH OH O HO O O OH O-Cellulose

OH

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Hemicelluloses

More

than one sugar Branched or substituted Short Reducing and nonreducing ends Generally not crystalline

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Xylan (1)
Primary

hemicellulose in hardwoods Linear chain backbone of xylose units Substituents are 4-O-methylglucuronic acid, acetate groups and, in some, arabinose Substituents prevent crystallization, but may be removed during pulping and bleaching

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Xylan (2)
O O 4 HO O HO H3CO HOOC OH O O 1

OH
4

OH O

1 O
O

1 O O O 3 OH 1 4

OH

OH O

O OH HOH2C OH 1

4-D-Xylp-1

4-D-Xylp-1 2

4-D-Xylp-1

4-D-Xylp-1 3

4-D-Xyp-1 5

1 4-O-Me-D-Glc pA 2

1 -L-Araf

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Glucomannan (1)
Chief

hemicellulose component of softwoods Straight chain backbone of mannose units and a smaller number of glucose units More vulnerable than xylan to chemical degradation

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Glucomannan (2)
HOH 2C O O 4 HO OH 1 O 4 RO OR O 1 O HOH 2C 4 RO 1 O OR RO O 4 1 HOH 2C OR O

O
OH O 1

HO HOH 2C HO

4- D-Glcp -1

4- D-Man p -1 6

4- D-Man p -1 2,3

4- D-Man p -1

1 -D-Galp

Ac

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Lignin
Native

lignin is a polymer of coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol


HO 1 6 5 R2 4 OH 2 3 R1 Coniferyl alcohol/guaiacyl: R1 =OMe, R2 =H Sinapyl alcohol/ syringyl: R1=R2 =OMe p Coumaryl alcohol: R 1 =R2 =H

A

heterogeneous, branched and cross-linked polymer with phenylpropane units linked by C-C and C-O bonds Cross-linked with polysaccharide chains
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Beta-O-4 Linkage

SW: 50% HW: 60%

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Alpha-O-4 Linkage

SW: 2-8% HW: 7%

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5-5 Linkage

5 - 20%

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4-O-5 Linkage

SW: 4% HW: 7%

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Beta-5, Beta-1 and Beta-Beta Linkages


SW: 9-12% HW: 6% SW: 7% HW: 7% SW: 2% HW: 3%

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Lignin Reactions During Kraft Pulping


Fragmentation

Alpha- and beta- aryl ether cleavage in free phenolic units Enol ether formation Alpha- and beta- aryl ether cleavage in etherified units C-C bond cleavage Condensation Bonding to carbohydrates Other reactions

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Alpha-Aryl Ether Cleavage in Free Phenolic Unit

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Beta-Aryl Ether Cleavage in Free Phenolic Units

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Enol Ether Formation

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Beta-Aryl Ether Cleavage in Etherified Units

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C-C Bond Cleavage

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Condensation: Competitive Addition of Nucleophiles to QMs

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Condensation with Formaldehyde

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Kraft Pulping Resistant Structures

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Quinone Formation During Kraft Pulping

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Lignin Carbohydrates Bonds

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Other Reactions: Formation of Stilbenes and Enol Ethers

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Residual Lignin Structure


Phenolic

hydroxyl groups Beta-aryl ethers C-C bonds Condensation products Functional group analysis Linkages to carbohydrates

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Phenolic Hydroxyl Groups in Dissolved and Residual Lignins


3.2 Phenolic hydroxyl content (mmol/g) 3.0 2.8 2.6 2.4 2.2 2.0 30 25 20 15 Unbleached kappa number 10 Kraft lignins Residual lignins

Phenolic hydroxyl content of various kraft (from black liquor) and residual lignins versus unbleached kappa number Froass, Peter M.; Ragauskas, Arthur J.; Jiang, Jian E. NMR studies. Part 3. Analysis of lignins from modern kraft pulping technologies. Holzforschung (1998), 52(4), 385-390. Froass, Peter M.; Ragauskas, Arthur J.; Jiang, Jian-er. Nuclear Magnetic Resonance Studies. 4. Analysis of Residual Lignin after Kraft Pulping. Industrial & Engineering Chemistry Research (1998), 37(8), 3388-3394

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Beta-Aryl Ethers in Residual and Dissolved Lignins


C in -O-4 (per aromatic unit) 0.22 0.20 0.18 0.16 0.14 0.12 0.10 30 25 20 15 Unbleached kappa number 10 Residual lignins Kraft lignins

Content of C in -O-4 structures for various kraft (from black liquor) and residual lignin versus unbleached kappa number

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Functional Groups in Lignin Wood/Pulp

Froass, Peter M.; Ragauskas, Arthur J.; Jiang, Jian-er. Chemical structure of residual lignin from kraft pulp. and Technology (1996), 16(4), 347-365.
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Journal of Wood Chemistry

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Hexenuronic Acid Formation

MeGlcA
H H3CO HO CO2H O

HexA
H HO2C O

+ O
xylan

CH3O-

O
OH Xylan

Kraft pulping

HO

OH

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