Lignin Chemistry

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Lignin Chemistry Production of Lignosulphonate
An Introduction

• Prepared by Craig Hogan
• LignoTech South-Africa
• Presented by Philip Chuah
• Borregaard SEA PL

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Topics

• Where lignin comes from
• What it looks like chemically
• Changing lignin to lignosulphonates
• Where its used

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Where lignin comes from

• Softwood Trees
• Cedar, Cypress, Fir, Hemlock, Larch, Pine,
  Redwood, Spruce, Thuja
• Hardwood trees
• Ash, Aspen, Beech, Birch, Elm, Eucalyptus,
  Hickory, Maple, Oak, Poplar, Walnut
• Grasses

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Where lignin comes from

• Cellulose (45)
• Hemicellulose (20 - 25)
• Lignin
• Softwood (27 - 37)
• Hardwood (16 - 29)

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Where lignin comes from

• Photosynthetic processes using chlorophyll in
  green leaves produce sugars
• CO2 H2O solar energy --gt sugars O2
• Sugars condense with dehydration to polymers
• sugars - H2O --gt cellulose and hemicellulose

• The shikimate and cinnamate biochemical pathways
  form the building blocks for the lignification
  processes
• sugar - H --gt shikimic acid --gt L-phenylalanine
  and L-tyrosine.
• L-phenylalanine and L-tyrosine --gt phenylpropene
  monomers.

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What lignin looks like chemically

• Phenylpropene monomers (1 3)

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What lignin looks like chemically

• Phenylpropene monomers (1 3)

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What lignin looks like chemically

• Phenylpropene monomers (1 3)

• Grasses 1 and 2 in varying amounts.
• Softwoods Almost exclusively 2.
• Hardwoods 2 and 3 in varying amounts.

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What lignin looks like chemically

• 2 electron reactions

• Ions are involved

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What lignin looks like chemically

• 1 electron reactions

• Free radicals are involved

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What lignin looks like chemically

• One electron, enzymatic dehydrogenation, e.g.
  coniferyl alcohol.
• Resonance stabilised phenoxy, aryl and aliphatic
  free radicals.

Ref E. Sjöström, Wood Chemistry, ISBN
0-12-647481-8
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What lignin looks like chemically

• Common linkages between phenylpropane units
  create ether linkages (R-O-R gt 2/3 of linkages)
  and carbon-carbon bonds (C-C lt 1/3 of linkages).

Ref E. Sjöström, Wood Chemistry, ISBN
0-12-647481-8
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What lignin looks like chemically
Linkage type Dimer Structure Percent of the total linkages Percent of the total linkages
Linkage type Dimer Structure Softwood Hardwood
?-O-4 Arylglycerol-?-aryl ether 50 60 a
?-O-4 Non-cyclic benzyl aryl ether 2 8 7
?-5 Phenylcoumaran 9 12 6
5-5 Biphenyl 10 11 5
4-O-5 Diaryl ether 4 7
?-1 1,2-Diaryl propane 7 7
?-? Linked through side chains 2 3
a About 40 of the coniferyl (guaiacyl) and 60 of sinapyl (syringyl) type. a About 40 of the coniferyl (guaiacyl) and 60 of sinapyl (syringyl) type. a About 40 of the coniferyl (guaiacyl) and 60 of sinapyl (syringyl) type. a About 40 of the coniferyl (guaiacyl) and 60 of sinapyl (syringyl) type.
Ref E. Sjöström, Wood Chemistry, ISBN
0-12-647481-8
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What lignin looks like chemically
Linkage type Dimer Structure Percent of the total linkages Percent of the total linkages
Linkage type Dimer Structure Softwood Hardwood
?-O-4 Arylglycerol-?-aryl ether 50 60 a
?-O-4 Non-cyclic benzyl aryl ether 2 8 7
?-5 Phenylcoumaran 9 12 6
5-5 Biphenyl 10 11 5
4-O-5 Diaryl ether 4 7
?-1 1,2-Diaryl propane 7 7
?-? Linked through side chains 2 3
a About 40 of the coniferyl (guaiacyl) and 60 of sinapyl (syringyl) type. a About 40 of the coniferyl (guaiacyl) and 60 of sinapyl (syringyl) type. a About 40 of the coniferyl (guaiacyl) and 60 of sinapyl (syringyl) type. a About 40 of the coniferyl (guaiacyl) and 60 of sinapyl (syringyl) type.
Hardwood - more
Softwood - more
Hardwood - more
Ref E. Sjöström, Wood Chemistry, ISBN
0-12-647481-8
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What lignin looks like chemically
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What lignin looks like chemically

• A segment of softwood lignin as proposed by Adler
  (1977).

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What lignin looks like chemically
Ketone group
Aldehyde group
Alicyclic group
Primary alcohol group
Secondary alcohol group
Alkene group
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• To you for your attention.

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Wood - source of lignin

• Composition of wood
• Cellulose (45 )
• Hemicellulose (20-25 )
• Lignin
• Softwood (27-37 )
• Hardwood (16-29 )

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Products from Wood Borregaard ChemCell and
Borregaard LignoTech
2.5 fm³ wood
1000 kg
Bio-fuel

• Cellulose 400 kg

Ethanol 50 kg CO² 45 kg
Vanillin 3 kg
Lignin 400 kg
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Borregaard ChemCell and Borregaard LignoTech
Wood based chemicals in an integrated concept
Bio energy (bark, side streams from the
production, biogas from the waste water treatment)
SPECIALITY-CELLULOSE
Drying machine
Bleeching plant
Wood
400 kg
1000 kg
Woodyard
Digester
Vanillin-plant (Yeast)
Lignin-plant
Etanol-plant
LIGNIN
400 kg
VANILLIN(Norway)
YEAST (Switzerland)
ETHANOL
CO2
50 kg
3 kg
20 kg
45 kg
Applications (end products) Cellulose Lignin
Vanillin Ethanol Yeast Construction
materials Concrete additives Food Car care Food
Cosmetics Animal feed Perfumes Paint/
varnish (taste enhancer) Food Dyestuff Pharmace
uticals Pharmaceutical industry Feed
(proteins) Tablets Oil-well additives Paint /
varnish Batteries Textiles Briquetting Paper
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Changing lignin to Lignosulphonate

• Digesters high pressure and temperature
• Acidic, metal bisulfite sulfonation reagents,
  e.g. calcium bisulfite and SO2

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Production of lignosulfonates
Prepared by Guro Elise Fredheim 11.09.06
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Raw material softwood and hardwood
Softwood Hardwood
Cedar Cypress Fir Hemlock Larch Pine Redwood Spruce Thuja Ash Aspen Beech Birch Elm Eucalytus Hickory Maple Oak Poplar Walnut
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Locations of Borregaard units
Softwood
Hardwood
Head office Production Sales/Rep. Office Regional
sales office
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Steps of the process ...
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Wood Source
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... Cutting ...
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... Transport ...
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... Renewable sources by Re-planting
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Borregaard LignoTech Production flow
Pulpingchemical
Wood chips
Digester
Pulp
Spent liquor
Chemicals/other rawmaterials
Powder
Spraydrier
BulkBagBig bag
Liquid
Bulk tankerContainer
Evaporation plant
Biological/Chemical/Physical processing
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Kamsahamnida -Thanks

• To you for your attention.