Dia 1 - Noppa

Wood Extractives
Both challenges and opportunities
Bjarne Holmbom
MSc course at Aalto University
Espoo 16.10. 2014
Outline
1. Terms, structures and chemical properties
2. Challenges in pulping and papermaking
3. Opportunities as specialty chemicals
B. Holmbom ÅA 16 Oct 2014
Forest Biorefineries
Bioenergy Biofuels
Wood Products
Pulp and Paper
High-value
biomaterials and biochemicals
Printing
Packaging
Tissue
Chemical markets
Food and Feed
Health
More value from the forest resources
B. Holmbom ÅA 16 Oct 2014
Historical products
 Amber – fossil oleoresin, in Baltic countries
from an extinct Araucaria species about 40 M
years ago
 Noah´s arch painted with ”pitch”
 Mummies in Egypt balsamed with resins
B. Holmbom ÅA 16 Oct 2014
Birch bark tar
Board of Antiquities
Eastern Finland
7000 B.C.
3 cm
GC - MS
Manufactured from birch outer bark
The first technochemical product (?)
The first chewing gum
Actually, already the Neandertals 40 000 years ago
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5
Wood tar
the most important product from Finland 1570 - 1850
For protection of wood products (ships and buildings), and health
B. Holmbom ÅA 16 Oct 2014
For one barrel:
8-10 full days of work
About 50 pine stems
Yield ~ 0.5%
B. Holmbom ÅA 16 Oct 2014
Wood extractives
products today
 Tall oil and turpentine in
the 1910´s
 Sitosterol in 1995
HO
Sitosterol
O
MeO
O
 HMR Lignan in 2006
HO
HO
 Emerging products ?
OMe
OH
B. Holmbom ÅA 16 Oct 2014
Turpentine
 Mainly the monoterpenes from oleoresin
 Recovered by condensation of digester relief
(crude sulfate turpentine)
 Purified by distillation
 Also from tapped or solvent-extracted
oleoresin, by steam distillation, so-called gum
and wood turpentine
B. Holmbom ÅA 16 Oct 2014
Dominating monoterpenes in turpentine
-Pinene
Bp. 155-156oC
-Pinene
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 3-Carene
Volatiles
To vacuum system
1
Crude
Turpentine
3
2
4
Plant in Oulu
Arizona Chemicals
Distillation
residue
B. Holmbom ÅA 16 Oct 2014
Pinene
(96% -pinene)
4
Dipentene
(60% carene)
Value From
The Tree
Aroma chemicals for
food, perfumes, cosmetics
Pine oil
Cleaners
Packaging
Adhesives
PSA’s
Polymer
Additives
α-Pinene
PSA’s
Specialty
Adhesives
NonWoven
Adhesives
β-Pinene
Crude Sulfate
Turpentine
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Anise
Flavoring
Solvents
Other
Distillates
Sulfate (kraft) soap
 Sulfate soap contains
 Fatty and resin acid soaps (RCOO-Na+) from
resin acids, free and esterifed fatty acids
 Neutral lipophilic compounds
 Black liquor
 The soap is boiled with sulfuric acid to
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CTO
Soap
To scrubber
Reactor
CTO
Decanter
H2SO4
Screen
Decanter
Fibre
material
Feed
tank
“Brine”
Na2SO4-solution
B. Holmbom ÅA 16 Oct 2014
Crude Tall oil (CTO)
 50% fatty acids, 40% resin acids, 10% neutrals (pine
wood)
 Less resin acids and more neutrals for pine-birch CTO
 Yield: 30-60 kg/ton pulp (1.5 – 3 % of wood)
 The crude tall oil is fractionated / refined by vacuum
distillation
B. Holmbom ÅA 16 Oct 2014
Water
Crude
Tall Oil
(CTO)
1
Gases
4
2
5
3
Plants in Oulu
(Arizona Chemicals)
and in Rauma
(Forchem)
Tall Oil
Pitch
(TOP)
Light
Oil
Tall Oil
Rosin
(TOR)
Distilled
Tall Oil
(DTO)
Tall Oil
Fatty Acids
(TOFA)
Value From The Tree
Paints
Coatings
Flexo ink
Solvents
Fuel
Additives
Adhesives
Packaging
NonWovens
Litho Ink
Gravure ink
Rubber
Chewing
Gum
TOFA
Rosin
Coatings
Lubricants
Emulsifiers
Corosion
Inhibitors
OreRefining
Rubber
Processing
Crude Tall Oil
DTO
World rosin consumption (2008)
HO
HO
Sitosterol
Sitosterol
Sitostanol
Blood and heart
HO
Cholesterol
Many sitosterol products




Raisio Group
Unilever: Becel pro-active
Teriaka: Diminicol
and other ---
Raisio Group
1995 -
Sitosterol production
 From tall oil soap at pulp mills, or from pitch at
tall oil distillation plants
 Plant in Kaukas 1977 - 2005
 Also from soybeans
 Global production now about 13 000 t/a (est.),
more than half from tall oil pitch
Burning - a threat or opportunity for tall oil ?
• Soap
or CTO have been burnt in many kraft pulp mills
• In 2010: “Green Diesel” from CTO (Sunpine AB)
• UPM-Kymmene starts production of Biodiesel in 2014
B. Holmbom ÅA 16 Oct 2014
Burning - a threat or opportunity for tall oil ?
• Soap
or CTO have been burnt in many kraft pulp mills
• In 2010: “Green Diesel” from CTO (Sunpine AB)
• UPM-Kymmene starts production of Biodiesel in 2014
There is not enough CTO available for these two plants
and for the three distillation plants in Finland and Sweden
More value created by distillation (?)
B. Holmbom ÅA 16 Oct 2014
In 1998, as it happened
We sampled a spruce knot
Analysis: it contained 10% of lignans !
The start for extensive research on knots
The knot story
Analysis
10% lignans !
1998
More spruce
knots
6-29% lignans
Knots from
other tree
species
60+ species
5-15% polyphenols
Technical
sep. of knots
”ChipSep”
Applications
Production
of knots
The spruce lignan
Hydroxymatairesinol (HMR)
O
MeO
O
HO
• 70-80% of lignans in spruce knots
HO
• Strong antioxidant
• Inhibits breast cancer growth
OMe
OH
(Univ. of Turku)
• Hormos Medical Corp., Turku, product development
• Clinical test on humans: no adverse effects
• New dietary ingredient clearance from US FDA 2004
• License Hormos  Linnea S.A. in 2005
• Production of knots (Separation Research)
26
The ChipSep Process
FI Pat Appl. 2000 by C. Eckerman and B. Holmbom
Pulping
Over-thick
chips
Rechipped
Chip
Dryer
Normal
wood
Sep. tank
Warm air
Knot material
27
Farm production of knots 2005 - 2007
Over-thick spruce chips
from a paper mill in Northern Finland
28
Spruce
wood
Chipping
Screening
TMP
Pulping
Over-thick chips
Bioenergy
ChipSep
Knot
material
Normal
wood
Ethanol
Raw extract
Precipitation
KAc
HMR Lignan
(KAc adduct)
29
www.hmrlignan.com
Recent research has shown that
plant lignans have a positive
influence on the development of
breast, prostate and colon
cancer which rely specifically on
oestrogens in order to progress.
Lignans also help to maintain
good cardiovascular health and
to moderate other oestrogendependent health problems
such as menopause symptoms
and osteoporosis.
Nutritional supplements
31
More products ! ?
 Approval for health food (EU ”Novel Foods”)
needed
 Ingredient in cosmetics
 Natural antioxidants / antimicrobials
32
Knots: the richest source of polyphenols in nature
O
MeO
MeO
OH O
O
HO
MeO
O
O
HO
HO
HO
OH
OMe
OMe
OMe
OH
OH
OH
HMR
Nortrachelogenin
Lariciresinol
O
MeO
OH
MeO
OH
O
HO
HO
OMe
OH
Secoisolariciresinol
OMe
OH
Matairesinol
In many species also
flavonoids
and stilbenes
Bioactive extractives from bark






Paclitaxel (Taxol®)
Pycnogenol®
Spruce resin salve
Stilbenes from spruce bark
Tannins
Betulinol and its derivatives
Paclitaxel (Taxol®)
 A chemotherapy drug for treatment of ovarian,
breast and lung cancer
 An alkaloid extracted from the bark and needles of
yew trees, Taxus species
 Since 1995, now sold for over one billion USD per year
 Extract from the bark of the
maritime pine tree growing in
southwest France
 A natural combination of
proanthocyanidins,
bioflavonoids and organic
acids
 A powerful antioxidant
 A natural anti-inflammatory
agent
Traditional chewing gum and
wound healing salve from spruce resin
 Spruce resin ”Überwallungsharz” has been chewed by
people in the boreal region since ancient times
 Probably a positive effect on oral health
 Same resin used traditionally also for wound healing,
mixed into butter
resin salve
Manufactured from pure spruce resin collected in Lapland.
Mixed into a fat-based salve, 10% resin.
Pressure ulcers
Burns
Wound infections
Surgical wounds
Psoriasis
Nail fungus
Approved by the National Agency for Medicines in
Finland in 2008, now sold in Finnish pharmacies
Developed and manufactured by Repolar Ltd
5-10 % stilbenes in spruce bark
OH
HO
HO
OH
Resveratrol
Also in red wine
OH
OH
HO
OH
OMe
OH
OH
Piceatannol
Me-Piceatannol
Resveratrol can extend the life-span of yeasts, banana flies, mice, etc.
Humans too ?
Birch outer bark
Betulinol
~ 30%
CH2OH
HO
Betulinol
1
Outer
bark
4
Inner
bark
Suberin
~ 30%
Polyester of
hydroxy fatty acids
Birch bark waste in Finland ~ 800,000 t/a
CH2OH
HO
COOH
HO
betulinol
betulinic acid
• Chemically stable, white product
• Ingredient in cosmetic creams
• Stabiliser for water-in-oil emulsions
• Several producers (USA, Germany, Russia)
Hydrophobization with birch outer bark extract
Holmbom & Holmbom 2013, EU AFORE project
B. Holmbom ÅA 16 Oct 2014
www.sepres.com
Hydrophobization with birch outer bark extract
1. Separation of outer bark from inner bark (grinding
and screening)
2. Extraction of outer bark, with e.g. ethanol, extract
rich in betulin(ol)
3. Spraying, dipping, surface coating of wood, paper,
paperboard or textile products
4. “Curing” redistribution of extractives, esp.
betulinol, through sublimation - redeposition
B. Holmbom ÅA 16 Oct 2014
www.sepres.com
Filter paper with birch bark extract
Hydrophobization with birch outer bark extract
B. Holmbom ÅA 16 Oct 2014
www.sepres.com
Trees are very special plants
 Live very long
 Through evolution during millions of
years      efficient
chemical defense systems (mostly
extractives)
 Richer in unique, bioactive
compounds than annual plants
Routes to valuable bioactive extractives
Tall Oil
Turpentine
Pulping
Knots
Bark
Sitosterol
Papermaking
Lignans
Flavonoids
Stilbenes
Stilbenes
Betulinol
Tannins
Paper
Board
Health-foods
Dietary suppl.
Pharmaceut.
Cosmetics
Techn. antiox.
Specialty products from extractives
Maybe not big business by volume
But may give profitable margins
And --- may also promote human health
in a natural way
Literature - Opportunities
•
•
•

•
•
•
•
•
Holmbom, B., Willfoer, S., Hemming J., Pietarinen, S., Nisula, S., Eklund, P. and Sjoeholm, R.
(2007) Knots in trees – a rich source of bioactive polyphenols. In: Materials, Chemicals and
Energy from Forest Biomass (Ed. D.S. Argyropoulos), ACS Symposium Series 954, ACS, pp.
350-362.
Holmbom, T. and Holmbom, B. (2014) A novel hydrophobisation technology utilising birch bark
extractives. Proceedings, Nordic Wood Biorefinery Conference, Innventia, Stockholm.
Holmbom, B. (2011) Extraction and utilisation of non-structural wood and bark components, In:
Biorefining of Forest Resources (Ed. R. Alén), Paperi ja Puu Oy, Helsinki 2011, pp. 178-224.
Holmbom, B., Sundberg, A. and Strand, A. (2010) Surface-active compounds as forestindustry by-products. In: Surfactants from Renewable Resources (Eds. M. Kjellin and I.
Johansson), John Wiley & Sons, Ltd, New York 2010, pp. 45-62.
Juvelius, E. (1747) Tiärtilwärkningen i Österbotn, Master´s Thesis, Åbo Akademi, Åbo.
Pietarinen, S.P., Willför, S.M., Ahotupa, M.O., Hemming, J. and Holmbom B.R. (2006)
Knotwood and bark extracts: strong antioxidants from waste materials. J. Wood Sci. 52:436444.
Tall Oil (Eds. J. Drew and M. Probst), Pulp Chemicals Association, New York 1981.
Välimaa, A-L., Honkalampi-Hämäläinen, U., Pietarinen, S., Willför, S., Holmbom, B. and von
Wright, A. (2006) Antimicrobial and cytotoxic knotwood extracts and related pure compounds
and their effects on food-associated micro-organisms. Int. J. Food Microbiol. 115(2): 235-243.
Willför, S., Hemming, J., Reunanen, M., Eckerman, C., and Holmbom, B. (2003) Lignans and
lipophilic extractives in Norway spruce knots and stemwood. Holzforschung 57(1), 27-36.
B. Holmbom ÅA 16 Oct 2014

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