Could biomass boilers be

operated at higher steam

efficiencies (higher temps.)?
Sandy Sharp (SharpConsultant, Columbia, MD)
Jim Keiser (Oak Ridge National Laboratory, Oak Ridge, TN)
Doug Singbeil (FPInnovations, Vancouver, BC, Canada)
Jim Frederick (Table Mountain Consulting, Golden, CO)
Curtis Clemmons, (MeadWestvaco, Covington, VA)
Laurie Frederick, (FPInnovations, Vancouver, BC, Canada)

Project tasks

Could existing alloys serve in biomass boiler SHs

at temperatures 100 Celsius degrees above
current operating temperatures?
1. Strategies for managing superheater corrosion
2. Lab and field tests of candidate alloys
3. Would value of the increased power generated
justify the costs of the increased steam
temperature?
2

Project funding and support

U.S. Department of Energy

Office of Energy Efficiency and Renewable Energy, Industrial

Oak Ridge National Laboratory

Budget: Research: 1,150,000 ($1,568,000); In-kind:
588,000; Total: 1,730,000 ($2,360,000)
Project partners (in-kind contributions): bo Akademi
University, Andritz Oy, Babcock & Wilcox, Catalyst Paper,
Chalmers University of Technology, Domtar Corporation,
E.ON UK, FM Global, FPInnovations, Foster Wheeler,
Georgia Institute of Technology, Haynes International, Howe
Sound Pulp & Paper, International Paper, MeadWestvaco,
Metso Power, Outokumpu Stainless, Rolled Alloys, Sandvik
Materials Technology, SharpConsultant, Southern Company,
Special Metals, Table Mountain Consulting, ThyssenKrupp
VDM, University of Toronto Pulp and Paper Centre, Vattenfall
Power and the Weyerhaeuser Company.

Technologies Program, contract DE-AC05-00OR22725 with

22

Advanced biomass boilers

achieve higher steam
temperatures using

Modified boiler designs

Fuel modifications or chemical additions
Corrosion-resistant superheater alloys

Design modification 1a:

Remove deposits before SH
Add an empty pass between furnace and SH

Iglesta CHP boiler

Sdertlje, Sweden
(wood and waste)

Design modification 1b:

Remove deposits before SH
Add a Chlorine trap upstream of the SH
Molten outer layer of ash may restrict penetration of
corrosives

WTE boiler, Schweinfurt, Germany

Straw-fired boilers (Marib, Avedre 2, Denmark; Gren, Norway) also
operate with molten outer layer of SH ash

Design modification 2: Move

CFB SH from flue gases into
recirculated fluidizing medium
Foster
Wheeler
INTREX

Metso
(Valmet)
CYMIC

Lurgi FBHE

Design modification 3: Move

SH outside boiler and heat it
with a less-corrosive fuel

Ensted (benr, Denmark) straw/wood fired boiler raised SH temperature

from 470C to 542C by installing an external wood-fired SH

Design modification 4::Design

SH for very rapid replacement

WTE boiler, City of Amsterdam, The Netherlands, with KEMA

Design modification 5: Operate

SH above ash dew point temp.
Raise tube surface temperature to convert NaCl
deposits to less-corrosive HCl(g)

Palonen et al., 2009:

Norrkping, Langerbrugge, etc.
Skog, et al., 2008

10

Process modification 1:
Dilute corrosive biofuels

Simplest approach: dilute corrosive biofuels

with less corrosive fuel

e.g. diluting straw with 80% coal does not

significantly increase SH corrosion
11

Process modification 2:
Wash corrosives out of
biofuels

Water-soluble alkali chlorides are among the

most corrosive species faced by biomass boiler
SHs

Water leaching removes >80% of K, Na; >90% of Cl

from biomass crop fuels
But drying wet fuels can be expensive
12

Process modification 3:
Convert chlorides to sulfates
K2SO4 deposits are much less corrosive than
KCl because they have a higher melting temp. 1,069C rather than 770C
Sulfation reduces conversion of Cr2O3 to alkali
chromate:
can halve the corrosion rate
can be achieved by SO2 or SO3
2KCl(s) + SO2(g) + O2(g) + H2O K2SO4(s) + 2HCl(g)
e.g. WTE boiler, Norrkping, Sweden
(NH4)2SO4 SO3 + 2NH3 + H2O
(ChlorOut)

13

Process modification 4:
Convert chlorides to silicates

Silica or kaolinite additives react with alkali

chlorides to form alkali silicates or alkali
aluminum silicates
silicates have much higher melting
temperatures, reduce SH fouling and
corrosion
e.g. KCl concentrations in FBHE of Gren CFB
boiler (co-firing straw/coal) were reduced by two
OOMs by silica or kaolinite additions

14

Alloy modifications: use more

corrosion-resistant SH alloys
Alloy rankings depend on biomass fuel,
operational parameters, tube temps.
Corrosion rates
increase rapidly at
ash melting temp.

15

Conclusions of tasks 1, 2
SH corrosion control strategies and alloy
rankings had been developed for boilers burning
wood, straw, black liquor and municipal wastes
3 empirical models had been developed to
predict fouling and corrosion in biomass boilers

Fuel composition is used to predict ash composition;

(T - FMT) to predict fouling tendency;
field data to predict corrosion rate

In each of 4 challenging biomass boiler

environments, some alloys could have useful
lives at 100 Celcius degrees above current limits

16

Is the juice worth the

squeeze?

Use Rankine cycle software to calculate value

of additional power that could be generated by
operating typical biomass boilers at higher
steam conditions without changing fuel or firing
conditions
Compare the value of this additional power with
the costs of installing more corrosion-resistant
superheater alloys, using fuel additives or
changing the boiler design
2

Underlying principle

Availability of energy in steam (ability to do work) increases

with increasing steam temperature
Specific Available
Energy, kJ/kg

1800
100 bars
50 bars

1600

1400

1200

400

500

600

700

Temperature, C

Increasing our steam temperature by 100 Celsius degrees

will increase the energy available from a biomass fuel by
11.4% at 100 bars and 11.0% at 50 bars

Project collaborators
supplied steam data for
five biomass boilers
Two Black Liquor Recovery Boilers (52,54 MW)

Typical data from a boiler manufacturer

Process simulation model of 1,500 ODT pulp mill
Three wood-fired Biomass Boilers (27,28,43 MW)
West Coast pulp mill unit firing sea-floated logs
West Coast pulp mill unit firing 2/3 beetle-killed
pine, 1/3 sea-floated logs, some construction waste
Recently constructed BFB firing wood waste
6

Value of increased power in

5 biomass-fueled boilers
Recovery Boilers

Biomass Boilers

Conditions
B

@$40/MWh

+$1.54m

+$2.52m/y

+$2.94m/y

+$1.33m/y +$1.26m/y

@$80/MWh

+$3.08m

+$5.05m/y

+$5.89m/y

+$2.66m/y +$2.52m/y

@$40/MWh

+$2.45m/y

+$4.45m/y

+$5.61m/y

+$2.60m/y +$2.42m/y

@$80/MWh

+$4.91m/y

+$8.90m/y +$11.21m/y +$5.19m/y +$4.84m/y

+50C steam

+100C steam

Potential costs of maintaining process steam flows in biomass

boilers (likely not large) are not included in these calculations

16

Could value of increased

power generation justify cost
of increasing steam temps by
100 Celsius degrees?
Value of additional power generated from hotter
steam at constant firing conditions could pay:
$5,378/m - $24,911/m for 2,250 m for more
corrosion-resistant SH tubes replaced every 5
years (45p x 10t x 5m)
$2,420,000 - $11,210,000 per year to remove
corrosives from biomass fuel or to apply additives
$12m - $56m over 5 years to redesign boiler,
upgrade steam turbine
17

Project results are available

in 7 publications
Energy From Biomass Lessons From European Boilers
Sharp, Singbeil & Keiser, TAPPI PEERS conference, 2011
Superheater Corrosion Produced By Biomass Fuels
Sharp, Singbeil & Keiser, Paper 1308 at NACE Intl. Corrosion/2012 conference
Superheater Corrosion In Biomass Boilers: Todays Science and Technology
Sharp, Oak Ridge National Laboratory TM-2011/399, 2012
Performance of Alternate Superheater Materials in a Potassium-Rich Recovery
Boiler Environment
Keiser, Sharp, Singbeil, Frederick & Clemmons, TAPPI J, 12 (7), 45-56, 2013
Could Biomass-Fueled boilers be Operated at Higher Steam Temperatures?
1. Laboratory Evaluation of Candidate Superheater Alloys
Singbeil, Frederick, Keiser & Sharp, TAPPI Journal, to be published June 2014
Could Biomass-Fueled boilers be Operated at Higher Steam Temperatures?
2. Field Tests of Candidate Superheater Alloys
Keiser, Sharp, & Singbeil, TAPPI Journal, to be published June 2014
Could biomass-fueled boilers be operated at higher steam temperatures?
3. Initial analysis of costs and benefits
Sharp, Frederick, Keiser & Singbeil, TAPPI Journal, to be published June 2014

Measuring corrosion rates is

difficult

Sample temps.
are not constant
Corrosion is
irregular
How many cross-sections?
Max. or avg. metal loss beneath original surface?
Image analysis of cross-sections of lab test specimens
produced 28,800 measurements
25

Corrosion tests

Example of field corrosion data

Covington Recovery Boiler

Average Exposure Temperature (C)

650

600

S31009

Goal

550

N07214
N08028

500

N06025

Current
max T

450

N08120
S21500

400

S34709
N12160

350

N06690
300
-0,1

0,1

0,3

0,5

0,7

0,9

1,1

Total Material Affected (mm)

1,3

1,5

Nine alloys were selected

for exposure in the RB
corrosion probe
Alloy

UNS
number

Fe

Ni

Cr

Mo

310H SS

S31009

Bal

19.10

24.30

0.25

Haynes 214

N07214

3.56

Bal

16.08

Sanicro 28*

N08028

35

31

27

602CA

N06025

9.60

62.20

25.30

HR160

N12160

0.63

Bal

28.00

Inconel 690*

N06690

62

29

HR120

N08120

36.26

36.68

24.74

0.07

Esshete 1250*

S21500

72

10

15

347H SS

S34709

Bal

9.02

17.21

*Nominal values

Co

Mn

0.03
3.5

Al

4.22
1.8

2.30
0.27

30.20

Si

0.55

0.045

0.12

0.04

0.2

0.01

0.03

0.170

2.75

0.056

Other

Y=.004, Zr=.011

Y=0.07, Zr=0.09

0.02
0.11

0.16
6.3

0.73

0.057

N=0.21

0.5

0.1

Nb=1, V=2.5,
B=0.006

0.57

0.048

Conclusion from field and

Covington Recovery Boiler
lab tests
Average Exposure
Temperature (C)

650
600
550
500
450
400
350
300

0,5

1,5

S3100
9
N0721
4
N0802
8
N0602
5
N0812
0
S2150
0

Total Material Affected (mm)

In SH environments simulating boilers burning

sea-floated logs w and w/o demolition waste

coal-wood blends
kraft black liquor

existing alloys could serve useful lives in

superheaters operating 100 Celcius degrees
above current operating temperatures

29