Towards co-production of chemicals, power and fuels in ... · Boiler Committee. Academy of Finland...

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


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


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


Future

Pulp

Mill

•

Pulp•

Ethanol

•

Liquid

fuels

•

Specialty

chemicals•

Clean

power


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


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


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


Spruce bark: stilbenes and tannins

Sprucebark Residue

SequentialExtraction

Stilbenes5-10%

Tannins10-20%

Carbo-hydrates10-20%

Spruce bark waste in Finland ~ 700,000 t/a


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


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


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.

Presenter�

Presentation Notes�

�


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


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


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


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


•

Functional

foods•

Cosmetics

(sun

creams)

•

Technical

antioxidants•

Natural

biocides

More

polyphenol products?


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


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


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


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

________________________________________________________________________________________________________________


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


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”


Typical Recovery Boiler Steam System


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


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


Corrosion

Test

by

Alkali Salts

Beforeheattreatment

After

heattreatment

Preparedfor SEM


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)


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)


Additional Superheating in a Separate Furnace Fired with Clean Fuels

• Natural gas• Bark gasif. gas• Methanol


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


Gasification

•

20+ different

reactor

concepts

suggested

•

MTCI fluidized bed steam reformer

•

Chemrec entrained-flow gasifier


MTCI Black Liquor Steam Reformer (ca. 1987-present)

Product Gas + Air

Black Liquor

Product Gas

Flue Gas

Fluidizing SteamBed Solids

PulsedCombustors


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


Gasification

-

Challenges

•

Complete

carbon

conversion•

Cleaning

of the gases

•

Handling

of the cooking

chemicals

(Na, S)•

Reactor

materials

•

Non-process

elements

and emissions•

…


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


•

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


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!


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


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


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

Towards co-production of chemicals, power and fuels in ... · Boiler Committee. Academy of Finland...

Documents

Transcript of Towards co-production of chemicals, power and fuels in ... · Boiler Committee. Academy of Finland...