Chemistry of Kraft Pulp

The Chemistry of Wood and Kraft Pulping
ragauskas@hotmail.com
Typical Composition of Wood

Cellulose (41-53%) Hemicellulose (25-41%) Lignin (16-33%) Extractives (2-5%) Inorganics (<1%) Nitrogen compounds (traces)
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
Cellulose (1)
One
sugar Linear Long Reducing and nonreducing ends Partly crystalline
Cellulose (2)
OH O O HO OH O O HO OH
OH O HO OH OH O HO O O OH O-Cellulose
OH
Hemicelluloses
More
than one sugar Branched or substituted Short Reducing and nonreducing ends Generally not crystalline
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
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
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
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
10
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
11
Beta-O-4 Linkage
SW: 50% HW: 60%
12
Alpha-O-4 Linkage
SW: 2-8% HW: 7%
13
5-5 Linkage
5 - 20%
14
4-O-5 Linkage
SW: 4% HW: 7%
15
Beta-5, Beta-1 and Beta-Beta Linkages

SW: 9-12% HW: 6% SW: 7% HW: 7% SW: 2% HW: 3%
16
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

17
Alpha-Aryl Ether Cleavage in Free Phenolic Unit
18
Beta-Aryl Ether Cleavage in Free Phenolic Units
19
Enol Ether Formation
20
Beta-Aryl Ether Cleavage in Etherified Units
21
C-C Bond Cleavage
22
Condensation: Competitive Addition of Nucleophiles to QMs
23
Condensation with Formaldehyde
24
Kraft Pulping Resistant Structures
25
Quinone Formation During Kraft Pulping
26
Lignin Carbohydrates Bonds
27
Other Reactions: Formation of Stilbenes and Enol Ethers
28
Residual Lignin Structure

Phenolic
hydroxyl groups Beta-aryl ethers C-C bonds Condensation products Functional group analysis Linkages to carbohydrates
29
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
30
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
31
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.
Journal of Wood Chemistry
32
Hexenuronic Acid Formation
MeGlcA
H H3CO HO CO2H O
HexA
H HO2C O
+ O
xylan
CH3O-
O
OH Xylan
Kraft pulping
HO
OH
33

Chemistry of Kraft Pulp

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Chemistry of Kraft Pulp

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The Chemistry of Wood and Kraft Pulping

Typical Composition of Wood

Compositions of Several North American Pulpwood Species

sugar Linear Long Reducing and nonreducing ends Partly crystalline

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

SW: 50% HW: 60%

SW: 2-8% HW: 7%

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

Lignin Reactions During Kraft Pulping

Alpha-Aryl Ether Cleavage in Free Phenolic Unit

Beta-Aryl Ether Cleavage in Free Phenolic Units

Enol Ether Formation

Beta-Aryl Ether Cleavage in Etherified Units

C-C Bond Cleavage

Condensation: Competitive Addition of Nucleophiles to QMs

Condensation with Formaldehyde

Kraft Pulping Resistant Structures

Quinone Formation During Kraft Pulping

Lignin Carbohydrates Bonds

Other Reactions: Formation of Stilbenes and Enol Ethers

Residual Lignin Structure

Phenolic Hydroxyl Groups in Dissolved and Residual Lignins

Beta-Aryl Ethers in Residual and Dissolved Lignins

Functional Groups in Lignin Wood/Pulp

Journal of Wood Chemistry

Hexenuronic Acid Formation

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