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 ragauskas@hotmail.com 4 .

Cellulose (2) OH O O HO OH O O HO OH OH O HO OH OH O HO O O OH O-Cellulose 1 4 OH n ragauskas@hotmail.com 5 .

com 6 .Hemicelluloses More than one sugar Branched or substituted Short Reducing and nonreducing ends Generally not crystalline ragauskas@hotmail.

arabinose Substituents prevent crystallization. in some.com 7 . acetate groups and.Xylan (1) Primary hemicellulose in hardwoods Linear chain backbone of xylose units Substituents are 4-O-methylglucuronic acid. but may be removed during pulping and bleaching ragauskas@hotmail.

Xylan (2) O O 4 HO O HO H3CO HOOC OH O β O 1 OH 4 OH O 1 O O 4 1 O O O 3 OH 1 4 OH OH β O 1 O OH HOH2C OH 1α α 4-β−D-Xylp-1 4-β−D-Xylp-1 2 4-β−D-Xylp-1 4-β−D-Xylp-1 3 4-β−D-Xyp-1 5 1 4-O-Me-α−D-Glc pA 2 1 α-L-Araf ragauskas@hotmail.com 8 .

com 9 .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 ragauskas@hotmail.

Glucomannan (2) HOH 2C O O 4 HO OH β 1 O 4 RO OR O 1 O HOH 2C 4 RO 1 O OR RO O 4 1 HOH 2C OR O β O O OH O 1 α 6 HO HOH 2C HO 4-β− D-Glcp -1 4-β− D-Man p -1 6 4-β− D-Man p -1 2.3 4-β− D-Man p -1 1 α-D-Galp Ac ragauskas@hotmail.com 10 .

sinapyl alcohol.Lignin Native lignin is a polymer of coniferyl alcohol. branched and cross-linked polymer with phenylpropane units linked by C-C and C-O bonds Cross-linked with polysaccharide chains ragauskas@hotmail. and p-coumaryl alcohol HO β γ α 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.com 11 .

com 12 .Beta-O-4 Linkage SW: 50% HW: 60% ragauskas@hotmail.

Alpha-O-4 Linkage SW: 2-8% HW: 7% ragauskas@hotmail.com 13 .

20% ragauskas@hotmail.com 14 .5-5 Linkage 5 .

com 15 .4-O-5 Linkage SW: 4% HW: 7% ragauskas@hotmail.

com 16 .Beta-5. Beta-1 and Beta-Beta Linkages SW: 9-12% HW: 6% SW: 7% HW: 7% SW: 2% HW: 3% ragauskas@hotmail.

aryl ether cleavage in etherified units C-C bond cleavage Condensation Bonding to carbohydrates Other reactions ragauskas@hotmail.and beta.and beta.com 17 .Lignin Reactions During Kraft Pulping Fragmentation Alpha.aryl ether cleavage in free phenolic units Enol ether formation Alpha.

Alpha-Aryl Ether Cleavage in Free Phenolic Unit ragauskas@hotmail.com 18 .

com 19 .Beta-Aryl Ether Cleavage in Free Phenolic Units ragauskas@hotmail.

com 20 .Enol Ether Formation ragauskas@hotmail.

Beta-Aryl Ether Cleavage in Etherified Units ragauskas@hotmail.com 21 .

C-C Bond Cleavage ragauskas@hotmail.com 22 .

Condensation: Competitive Addition of Nucleophiles to QM’s ragauskas@hotmail.com 23 .

com 24 .Condensation with Formaldehyde ragauskas@hotmail.

com 25 .Kraft Pulping Resistant Structures ragauskas@hotmail.

Quinone Formation During Kraft Pulping ragauskas@hotmail.com 26 .

com 27 .Lignin Carbohydrates Bonds ragauskas@hotmail.

Other Reactions: Formation of Stilbenes and Enol Ethers ragauskas@hotmail.com 28 .

Residual Lignin Structure Phenolic hydroxyl groups Beta-aryl ethers C-C bonds Condensation products Functional group analysis Linkages to carbohydrates ragauskas@hotmail.com 29 .

. Peter M..com 30 . 385-390. Jiang. Part 3. Jian-er. Arthur J.Phenolic Hydroxyl Groups in Dissolved and Residual Lignins 3. Analysis of lignins from modern kraft pulping technologies.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. Ragauskas. 3388-3394 ragauskas@hotmail.. Ragauskas. 52(4).4 2. Industrial & Engineering Chemistry Research (1998). Holzforschung (1998). Arthur J.2 Phenolic hydroxyl content (mmol/g) 3. NMR studies. Peter M.2 2. Nuclear Magnetic Resonance Studies. Froass. 37(8).0 2.8 2. 4. Jian E.6 2.. Jiang. Analysis of Residual Lignin after Kraft Pulping.

22 0.14 0.com 31 .10 30 25 20 15 Unbleached kappa number 10 Residual lignins Kraft lignins Content of Cγ in β-O-4 structures for various kraft (from black liquor) and residual lignin versus unbleached kappa number ragauskas@hotmail.20 0.16 0.18 0.Beta-Aryl Ethers in Residual and Dissolved Lignins Cγ in β-O-4 (per aromatic unit) 0.12 0.

com Journal of Wood Chemistry 32 . Jiang. Arthur J. Peter M. 16(4). Ragauskas. 347-365... Jian-er. Chemical structure of residual lignin from kraft pulp. ragauskas@hotmail.Functional Groups in Lignin Wood/Pulp Froass. and Technology (1996).

Hexenuronic Acid Formation MeGlcA H H3CO HO CO2H O HexA H HO2C O + O xylan CH3O- O OH Xylan Kraft pulping HO OH ragauskas@hotmail.com 33 .