By-products from pulping of wood and non-wood raw ...fibrafp7.net/Portals/0/7_Niemela.pdf · and...
Transcript of By-products from pulping of wood and non-wood raw ...fibrafp7.net/Portals/0/7_Niemela.pdf · and...
By-products from pulping of wood
and non-wood raw materials
Important source of biomass chemicals
FIBRA seminar, March 23rd, 2015
Klaus Niemelä
VTT Technical Research Centre of Finland
2 28/5/2012
Examples of early (chemical) wood industries
Naval strores production (turpentine, resin)
Thermal processes
Tar production & by-products
Wood distillation industry (methanol, acetic acid etc)
Charcoal manufacture (important e.g. in Sweden for steel
industry in the 19th century – impacts on pulping byproducts)
Oxalic acid manufacture by alkali
fusion of sawdust in the past
3 28/5/2012
(Hard)wood distillation industry
The first industrial large-scale wood biorefinery process
Main operation period c. 1840-1920s/1930s
New plants constructed still in the 1950s/1960s, even later
The only industrial source for methanol and acetone until
1910s/1920s
Main source for acetic acid
Many other products also isolated
4 28/5/2012
Pulp mill biorefineries: pulp, chemicals, biofuels
Pulping process
Harvesting residues
AgromaterialsRecovered paper
Process(es)
Integratedpower/energyproduction
Processstreams
Pulp, paper
Energy
Biofuels
Chemicals
Chips
5 28/5/2012
Current share of pulping methods (for 190-200 Mt pulp)
440 40
very many
40
Number of pulp mills
(10 pre-
hydrolysis
mills)
No organosolv processes
industrially operating
6 28/5/2012
Alkaline (kraft and soda) pulping:
Composition of material dissolved into spent liquors
(>130 million tons annually)
7
Distribution of black liquor organics
Softwood Hardwood
7 28/5/2012
Industrial by-products from alkaline pulping processes
(kraft and soda)
Currently
Turpentine (chemicals, parfymes, vitamins, polymers…)
Tall (pine) oil for fatty acids, resin acids, phytosterols
Lignin
In the past (only)
Methanol, ammonia
Heat treatment products (acetone, 2-butanone, oils…)
Dimethyl sulphide, dimethyl sulphoxide, dimethyl sulphone
From the prehydrolysis/extraction-kraft processes (past)
Xylose, furfural, hexoses, ethanol, yeasts…
Polysaccharides
10 28/5/2012
Methanol
Found in pyroligneous acid (wood distillation) in 1812
Produced in the late 1800s and early 1900s only by dry
distillation of (hard)wood
Discovered from kraft pulping streams 1908
In 1912, 5 Swedish mills recovered methanol!
The production peak in Sweden was in the 1930s (500 t/a)
Isolated at 3 Finnish mills in 1912-1924
No information found on production outside Scandinavia
Nowadays crude methanol produced from foul condensate
stripper off-gases (mainly for combustion)
11 28/5/2012
First mill-scale purification system recently started at
Al-Pac, Canada, based on 2-step distillation
13 28/5/2012
Ammonia as a by-product
Isolation integrated into the separation of turpentine and methanol
The method was developed by Alfons Hellström (1877-1965)
Applied only at Kotka mill, Finland (in the 1910s)
The production peak was in 1917, 8 tons of ammonium sulfate
14 28/5/2012
Erik Ludvig Rinman
1874-1937
Pulp mill biorefinery pioneer
(started in Sweden),
whose efforts accelerated
a lot of studies that still
go on…
15 28/5/2012
Heat treatment of black liquor, discovered by Rinman to increase
the formation of useful volatile compounds (kg/t pulp)
Promising early yields were approximately:
Methanol 30 kg
Acetone 20 kg
2-Butanone 20 kg
Light oils 18 kg
Heavy oils 50 kg
Industrial-scale process – Rinman method – operated at a German
pine soda pulp mill 1922-1929. Was not economically a big success,
for technical reasons and for discovery of methanol synthesis.
16 28/5/2012
Production at Regensburg, 1927-1929
Methanol 110 t
Acetone 49 t
2-Butanone 47 t
Light oil 56 t
Heavy oil 198 t
17 28/5/2012
The Rinman process had a huge impact on studies
on pulping spent liquor utilisation
Acids
Phenols
Ketones, etc
Heat treatments
Oxidations
Gasifications, etc
Still going strong for the
same products
18 28/5/2012
DMSO – Dimethyl sulphoxide (via DMS)
More valuable product from black liquor processing
Pilot-scale production in Finland from
black liquor in the 1940s
Knowledge transferred to the USA,
wher production from the 1960s to
2010. During the recent years, c. 1/3
of global DMSO was from black liquor
Also produced in the Soviet Union
(1974-1990s)
19 28/5/2012
Tall oil (pine oil)
Isolated at numerous softwood kraft pulp mills worldwide
Distilled at >20 distilleries to different fatty and resin acid fractions
(and residues)
Phytosterols also isolated in many countries
Production figure steady: 1,4-1,5 million tonnes
The main fractions are valuable products
Recent interest also for the manufacture of biodiesel
Softwood (tall oil and gum rosin) are the only sources of pine rosin
24 28/5/2012
Kraft (sulphate) lignins
Annual "production" over 60 million tons.
Used as a chemical/material: under 150,000 tons.
Dominating company: MeadWestwaco, USA
New and planned isolation capacity in the US, Canada, Finland…
25 28/5/2012
Kraft lignin (potential) uses
Phenolic resins
Panelboard adhesives
Thermoset resins for moulded products
Friction materials
Adsorbent materials
Foundry resins
Insulation materials
Decorative laminates
Rubber processing
Antioxidant applications
Printed circuit board resins
Animal health applications
Composites and biocomposites
Carbon fibres (for vehicles and other uses)
Synthetic lignosulphonates, with a large number of well-established uses
29 28/5/2012
Pre-extraction/hydrolysis before pulping
• Aim to recover a substantial part of hemicelluloses (xylan,
glucomannan) as polymers or monomers
• Pulp properties should not be affected
• A lot of interest in Europe and North America
• Sugars to be fermented to ethanol, or succinic acid (150,000 tons
of ethanol expected in 400,000-ton softwood pulp mill), or other
chemicals
• Method applied in the 1970s to isolate arabinogalactan before
pulping of larch wood chips (St. Regis company, products known
as Stractan)
30 28/5/2012
Prehydrolysis-kraft pulping for the prouction of dissolving pulp
From the prehydrolysate, isolated or produced at several mills in
the 1960s-1990s (water prehydrolysis)
Furfural
Xylose
Ethanol
Fodder yeast (e.g. 20,000 t/a
at Bratsk, USSR)
Today water vapor
hydrolysis used
33 28/5/2012
Lignosulphonates - production
Annual "production" over 4-5 million tons.
Used as a chemical/material: 1.8 million tons.
Production in Europe, Asia, North and South America, Africa.
Several companies operating, LignoTech dominating.
35 28/5/2012
Vanillin from lignosulphonates
Today, 15% of global vanillin production is based on oxidation of
lignosulphonates
Two producers: Borregaard (Norway), Bailu Papers (China)
In the past, also produced in the US, Canada, Japan, USSR, Poland.
Many plants closed 1980-2000.
Isolated by-products include dehydrodivanillin, acetovanillone, and
calcum oxalate
36 28/5/2012
Carbohydrate-based products from sulphite spent liquors
Xylose, arabinose
Galactose, mannose, rhamnose
Fermentation products ethanol, torula yeast, pekilo protein,
ribonucleic acids
Some fermentations also use aldonic and uronic acids, and acetic
acid
Furfural
Acetic acid
The isolation of lignosulphonates and carbohydrate products offer
interesting full biorefinery concepts
37 28/5/2012
Isolation of acetic acid at Lenzing, Austria
Food-grade product
Furfural isolated at the
same time
43 28/5/2012
Lenzing biorefinery, Austria
The net calorific value corresponds to
abt. 220 kg fuel oil per t of pulp produced!
Dissolving
pulp
Acetic acid
Spent liquor Excess
energy
Beech wood
50%
Pulp
mill
39% Furfural
Xylose
11%
Source: H. Harms, FTP Conf. 2005
45 28/5/2012
Torula yeast and pekilo protein
Pekilo protein produced only at two plants in Finland (1970s-1980s)
Torula yeast currently produced at a few countries
47 28/5/2012
Semichemical pulp mills
High-yield pulp mills (hardwood) for corrugated board, NSSC
process originally developed in the US in the 1920s to pulp wood
from tannin extraction
Pioneering acetic and formic acid separation processes developed
in the USA and Finland
Extraction columns
for acetic acid
Sonoco 1958-1970s
Savon Sellu 1979-1991
48 28/5/2012
Chestnut extraction-pulping process
operated in Italy 1957-2009
NSSC
pulping
Hot water
extraction
Tannin
Chips Pulp
49 28/5/2012
Mechanical pulping processes
Due to the high pulp yield (85-98%), limited opportunities for by-
products exist
Sulfur-free TMP turpentine isolated at a few mills (US, Canada,
Sweden, Finland…)
Opportunities to isolate and utilise of galactoglucomannan from
CTMP process waters thoroughly studied (not in mill-scale)