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METLA Jubilee Seminar 20.3.2007 - M Hupa
Towards co-production of chemicals, power and fuels in future pulp mills
Mikko Hupa and Bjarne HolmbomÅbo Akademi
Process
Chemistry
CentreTurku, Finland
Jubilee Seminar in the occasion of the 90th anniversary of METLA -
The Finnish Forest Research InstituteTuesday, 20 March 2007
Marina Congress Center, Helsinki
METLA Jubilee Seminar 20.3.2007 - M Hupa
Kraft Pulp Mill
Digester
Chips
Pulp
Whiteliquor
Blackliquor
15% solids
NaOH Na2 S
Na2 CO3Na2 SO4
Recoveryboiler
Black liquor concentration
Smelt
BlackLiquor
75% solids
Flue gas
Na2 CO3Na2 SO4
Na2 CO3Na2 S
Causticizing
Greenliquor
Dissolvingtank
WaterNa2 CO3
Na2 S
CaCO3 CaOLimekiln
Steam turbine
Steam
(power)
Process steam
METLA Jubilee Seminar 20.3.2007 - M Hupa
The Paper Mill as a Biorefinery for Production of Transportation Fuels
Chips
Digester
Pulp
Hemicellulose
Hemicelluloseextraction
Fermentation
Ethanol
White liquor
Black liquor
Gasification
Syngascleaning
Syngasconversion
Synthesisgas
HydrocarbonsMethanol
METLA Jubilee Seminar 20.3.2007 - M Hupa
Future
Pulp
Mill
•
Pulp•
Ethanol
•
Liquid
fuels
•
Specialty
chemicals•
Clean
power
METLA Jubilee Seminar 20.3.2007 - M Hupa
round wood
stemwood chips
black liquor
forest
paper
com-bustion
ash
emissions
heat power
harvesting
debarking
chipping pulping
pulp
&
bark
pulpingchemicals
pulping chemicals
Kraft Pulp
Mill
METLA Jubilee Seminar 20.3.2007 - M Hupa
Kraft Pulp
Mill
& Biorefinery
round wood
stemwood
knots
chips
black liquor
forest
paper
com-bustion
----
ash
emissions
heat power
harvesting
debarking
chipping
extraction
pulping
pulp
&
bark
pulpingchemicals
extraction
P P
pulping chemicals
METLA Jubilee Seminar 20.3.2007 - M Hupa
Birch bark: betulinol and suberin
Outerbark
Innerbark
Betulinol~ 30%
Suberin~ 30%
CH2OH
OH
Betulinol
Polyester of hydroxy fatty acids
Birch bark waste in Finland ~ 500,000 t/a
1
4
METLA Jubilee Seminar 20.3.2007 - M Hupa
Spruce bark: stilbenes and tannins
Sprucebark Residue
SequentialExtraction
Stilbenes5-10%
Tannins10-20%
Carbo-hydrates10-20%
Spruce bark waste in Finland ~ 700,000 t/a
METLA Jubilee Seminar 20.3.2007 - M Hupa
Resveratrol
Spruce bark&
Red wine
OH
HO
Pinosylvin
Pine knots
OH
OH
HO
Stilbenes both in bark and knots
OH
OH
OH
HO
Piceatannol
Spruce bark
METLA Jubilee Seminar 20.3.2007 - M Hupa
Kraft Pulp
Mill
& Biorefinery
round wood
stemwood
knots
chips
black liquor
forest
paper
com-bustion
----
ash
emissions
heat power
harvesting
debarking
chipping
extraction
pulping
pulp
&
bark
pulpingchemicals
extraction
P P
pulping chemicals
METLA Jubilee Seminar 20.3.2007 - M Hupa
0.0 %0.1 %0.1 - 5 % 6 - 24%
Hydroxymatairesinol (HMR)
Lignans in Picea abies
70-85% of the lignans
O
OMeO
OH
OH
OMe
OH
Willför, S. et al. Holzforschung 57 (2003) 27-36
33 knots 7 trees
Heartw. Sapw.
METLA Jubilee Seminar 20.3.2007 - M Hupa
HMR from spruce knots
University of Turku & Åbo Akademi:
• Inhibits the growth of breast cancer
• Precursor to the active metabolite enterolactone
• Strong antioxidant
• Hormos Medical Inc., Turku 1997 -
• US-FDA approval as dietary supplement in May 2004
• 2005: Linnea S.A., Locarno, world-wide production and
marketing license
O
OMeO
OH
OH
OMe
OH
METLA Jubilee Seminar 20.3.2007 - M Hupa
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 oestrogen- dependent health problems such as menopause symptoms and osteoporosis.
www.hmrlignan.com
On the marketin 2006
METLA Jubilee Seminar 20.3.2007 - M Hupa
Paper mill in Northern Finland
Spruce chips
Farm in Southern FinlandSeparation of pure knots
Pure knot material
Linnea SA, LocarnoExtraction and purification
Dietary supplement markets
HMR in capsules
METLA Jubilee Seminar 20.3.2007 - M Hupa
MeO
OH
OH
OMe
OHOH
Secoisolariciresinol
In other tree species other lignans !
MeO
OH
O
OH
OH
OMe
Lariciresinol
O
O
OH
OMe
MeO
OH
OH
Nortrachelogenin
O
OMeO
OH
OH
OMe
OH
HMR
O
OMeO
OH
OH
OMe
Matairesinol
In many species alsoflavonoids
and stilbenes
Knots: the richest source of polyphenols in nature
METLA Jubilee Seminar 20.3.2007 - M Hupa
•
Functional
foods•
Cosmetics
(sun
creams)
•
Technical
antioxidants•
Natural
biocides
More
polyphenol products?
METLA Jubilee Seminar 20.3.2007 - M Hupa
Kraft Pulp
Mill
& Biorefinery
round wood
stemwood
knots
chips
black liquor
forest
paper
com-bustion
----
ash
emissions
heat power
harvesting
debarking
chipping
extraction
pulping
pulp
extraction
&
barkseparation
PP
P
pulpingchemicals
extraction
P P
pulping chemicals
METLA Jubilee Seminar 20.3.2007 - M Hupa
Black Liquor Recovery Boilers 1937-Daily Capacity
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
1935 1940 1945 1950 1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005
Delivery year
Cap
acity
, tds
/d
Maximum
METLA Jubilee Seminar 20.3.2007 - M Hupa
Flue
Gas
Emission Components100 %
1 %
1 ppm
1 ppb
-15
CO2 Carbon Dioxide
CO Carbon Monoxide / Cx Hy Hydrocarbons
PAH Polyaromatic Hydrocarbons
As, Cr, Ni, V, Pb, Cd, Hg,... Heavy Metals
Dioxins, Furans
SO2 Sulfur Dioxide / NO x Nitrogen Oxides-5
-10
0
METLA Jubilee Seminar 20.3.2007 - M Hupa
Black Liquor
Recovery
Boiler
Emissions
1970 1980 1990 2000+_________________________________________________________________________________________________________________________________________________________________
SO2 (ppm)
1500 500 100 ~ 0NOx
(ppm)
70 70
80
50Red. S (ppm) 300 200
5 ~ 0
Particulate
(mg/m3) 500 300 100
30
________________________________________________________________________________________________________________
METLA Jubilee Seminar 20.3.2007 - M Hupa
EU Directive on Incineration of Waste Containing Fuels
Heavy Metals
(”EDD”)
•
Hg
0.05 mg/m3n
•
Cd+Tl
0.05 mg/m3n
•
Sb+As+Co+Cr+Cu+Pb+Mn+Ni+V
0.5 mg/m3n
METLA Jubilee Seminar 20.3.2007 - M Hupa
H
Li
Na
K
Rb
Cs
Fr
Be
Mg
Ca
Sr
Ba
Ra
Sc
Y
La
Ac
Ce
Ti
Zr
Hf
Rf
Pr
V
Nb
Ta
Ha
Nd
Cr
Mo
W
Sg
Pm
Mn
Tc
Re
Ns
Sm
Fe
Ru
Os
Hs
Eu
Co
Rh
Ir
Mt
Gd
Ni
Pd
Pt
Uun
Tb
Cu
Ag
Au
Dy
Zn
Cd
Hg
Ho
B
Al
Ga
In
Tl
Er
C
Si
Ge
Sn
Pb
Tm
N
P
As
Sb
Bi
Yb
O
S
Se
Te
Po
Lu
F
Cl
Br
I
At
He
Ne
Ar
Kr
Xe
Rn
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
lanthanides
actinides
alkali metals alkaline
earth metals
noblegases
halogens
f-block transition metals
d-block transition metalss-block p-block
UuuUub Uuq Uuh Uuo
”EU Heavy Metals”
METLA Jubilee Seminar 20.3.2007 - M Hupa
Typical Recovery Boiler Steam System
METLA Jubilee Seminar 20.3.2007 - M Hupa
Steam
Temperatures
inBlack Liquor
Recovery
Boilers
0
50
100
150
200
250
300
350
400
450
500
550
1935 1940 1945 1950 1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005
Delivery year
Stea
m te
mpe
ratu
re, o
C
METLA Jubilee Seminar 20.3.2007 - M Hupa
History of Steam Conditions of Coal Fired Power Plants in Japan
Year of Initial OperationYear of Initial Operation
Steam pressure
Steam temperature
5
10
15
20
25
600600
550550
500500
450450
400400
Stea
m te
mpe
ratu
re (C
)
Stea
m p
ress
ure
( MPa
)St
eam
pre
ssur
e ( M
Pa )
‘‘5555 ‘‘6060 ‘‘6565 ‘‘7070 ‘‘9090 ‘‘9595 20002000
30
~~~~ ~~
Hekinan-Unit3
Tachibanawan-1
Isogo-New Unit1
610 C
~~~~ ~~
31.0
METLA Jubilee Seminar 20.3.2007 - M Hupa
Corrosion
Test
by
Alkali Salts
Beforeheattreatment
After
heattreatment
Preparedfor SEM
METLA Jubilee Seminar 20.3.2007 - M Hupa
450°C500°C
525°C550°C575°C600°C
Salt 5Salt 6
Salt 7Salt 8
Salt 9Salt 10
0
20
40
60
80
100
Cor
rosi
on l
ayer
thic
knes
s m
Steel: ATime: 168 h
Corrosion due to Alkali Salts
120
140
(Skrifvars et al. 2007)
METLA Jubilee Seminar 20.3.2007 - M Hupa
450°C500°C525°C550°C575°C600°C
0102030405060708090
100
Cor
rosi
on la
yer t
hick
ness
μm
Steel: CTime: 168 h
Corrosion due to Alkali Salts
Salt 5Salt 6
Salt 7Salt 8
Salt 9Salt 10
(Skrifvars et al. 2
007)
METLA Jubilee Seminar 20.3.2007 - M Hupa
Additional Superheating in a Separate Furnace Fired with Clean Fuels
• Natural gas• Bark gasif. gas• Methanol
METLA Jubilee Seminar 20.3.2007 - M Hupa
Gasification
Partial
oxidation
of biomass
into combustible gases
(H2
, CO, CH4
etc.)
•
Burning
of the gases
in GT for power, or
•
Use
of the gases
for synthesis
of hydrocarbons
etc. (F-T)
Kraft Pulp
Mill
& Biorefinery
round wood
stemwood
knots
chips
black liquor
forest
paper
com-bustion
----gasifica-
tion
ash
emissions
heat power
synthesis gas
P
biofuels (l)
harvesting
debarking
chipping
extraction
pulping
synthesis
pulp
extraction
&
barkseparation
PP
P
pulpingchemicals
extraction
P P
pulping chemicals
METLA Jubilee Seminar 20.3.2007 - M Hupa
Gasification
•
20+ different
reactor
concepts
suggested
•
MTCI fluidized bed steam reformer
•
Chemrec entrained-flow gasifier
METLA Jubilee Seminar 20.3.2007 - M Hupa
MTCI Black Liquor Steam Reformer (ca. 1987-present)
Product Gas + Air
Black Liquor
Product Gas
Flue Gas
Fluidizing SteamBed Solids
PulsedCombustors
METLA Jubilee Seminar 20.3.2007 - M Hupa
Chemrec BLGCC Process (ca. 1986-present)
Fuelgas
Green liquor
Condensate
Gasifier
Blackliquor
Oxygen
Absorber / Stripper
Gascooler
HRSG
Steam
Steam turbine
Gasturbine
S-rich gas
Water
Quench
METLA Jubilee Seminar 20.3.2007 - M Hupa
Gasification
-
Challenges
•
Complete
carbon
conversion•
Cleaning
of the gases
•
Handling
of the cooking
chemicals
(Na, S)•
Reactor
materials
•
Non-process
elements
and emissions•
…
METLA Jubilee Seminar 20.3.2007 - M Hupa
Kraft Pulp
Mill
& Biorefinery
round wood
stemwood
knots
chips
black liquor
forest
paper
com-bustion
----gasifica-
tion
ash
emissions
residuesheat power
synthesis gas
P
biofuels (l)
harvesting
recycling
debarking
chipping
extraction
pulping
synthesis
pulp
extraction
&
barkseparation
PP
P
pulpingchemicals
extraction
P P
pulping chemicals
METLA Jubilee Seminar 20.3.2007 - M Hupa
•
Complicated
molecular
structures
developed
by evolution during
millions of years
•
Not easily
synthesized
by chemists
•
Truly
”green”
chemicals
with ”Nature´s
Wisdom”
•
Small volumes, but
”healthy”
margins
Conclusions: Specialty
Chemicals
METLA Jubilee Seminar 20.3.2007 - M Hupa
Conclusions: Biorefinery Fuels
and Energy
•
Biorefinery concepts
highly
interesting
–
but not
yet
available
technology
•
Many
unresolved
technical
challenges
–
Much more
research
needed
•
Optimization: Ethanol
vs. synthetic
fuels
vs. power?
•
We
should
not
forget
longer-term, curiosity- driven
research!
METLA Jubilee Seminar 20.3.2007 - M Hupa
Wood discs from 2 meters height of a ~40-year-old Norway spruce tree were used.
N
E
S
W
One annual growth ring
(1994)
Annual growth rings in
different compass direction
Microtoming
Latewood Earlywood
Annual Ring Study -
Sampling
Pranovich et al. 2006
Earlywood Latewood
Annual Growth Ring
020406080
100120140160
0 1 2 3 4mm
Galactans
Mannans Pranovich et al. 2006
mg/kg wood
METLA Jubilee Seminar 20.3.2007 - M Hupa
0
200
400
600
800
1000
0 1 2 3 4
1994 WEST
EARLYWOOD LATEWOOD
mg/kg wood
mm
Ca
Calcium
Distribution
within
the Annual
Growth
RingP
ranovich et al. 2006
METLA Jubilee Seminar 20.3.2007 - M Hupa
Acknowledgements
Kevin Whitty, Kari Saviharju, Nikolai DeMartini, Thomas Grace, Jim Frederick
Markku Auer, Andrey Pranovich, Bengt-Johan Skrifvars, Christian Mueller, Mikael Forssén, Maria Zevenhoven
Åbo Akademi ChemCom Consortium: Andritz, Foster
Wheeler, Kvaerner Power, Metsä-Botnia, Vattenfall, International Paper
Finnish
Recovery
Boiler
Committee
Academy of Finland Centre
of Excellence
Program–
Åbo Akademi Process
Chemistry
Centre
Graduate School
in Chemical
Engineering (GSCE)
Tekes