Melting properties of the smelt, carry-

over particles and superheater deposits

in the recovery boiler
Daniel Lindberga, Rainer Backmana,b, Patrice
Chartrandc, Mikko Hupaa,

a) bo Akademi Process Chemistry Centre

b) Energy Technology and Thermal Process Chemistry
Ume University, Sweden
c) Centre de Recherche en Calcul Thermochimique, Montral, Canada
 Outline
Thermodynamic modeling of molten alkali salts
in the pulp and paper industry
Purpose and goal
Historical developments
Thermodynamic model

Recovery boiler smelt

Polysulfides

Carry-over particles and superheater deposits

Pyrosulfates

Summary
Thermochemistry and melting properties of inorganic
compounds in black liquor conversion processes
The formation and the existence of molten alkali salts is
of great importance in the recovery boiler
Behavior of the smelt
Formation of sticky deposits on superheaters
Corrosion of alloys in contact with a melt
Important reactions involving a molten phase
Na2SO4(l)+(2+2X) C(s) Na2S(l)+4X CO(g)+(2-2X) CO2(g)
Na2CO3(l) + NaBO2(l) Na3BO3(l) + CO2(g)
 GOAL
To predict the melting behaviour for the Na+,K+/CO32-,S2-,SO42-
,Cl-,S2O72-, Sn2- system in the recovery boiler at varying
Temperature, Pressure and Composition

Experiments
+ set of discrete data

Empirical equations (curve fits of experiments)

Thermodynamic models

( )
G = f T , P, nNa2 S , nNa2 SO4 , nNa2CO3 , nNaCl ... (For every phase)
G
G G
H = T S = i = i io = RT ln ai
1 T P ,ni ni T , P ,n ,n

T P ,ni
j k
 Thermodynamic modelling
Developments & Highlights (1)
1960-1964: Erik Rosn
Computerized calculations of multicomponent/
multiphase equilibrium of pressurized black liquor
gasification. Activity coefficients for Na2CO3-Na2S

1984: Pejryd & Hupa

Equilibrium modeling of furnace gas and smelt bed
Non-ideal interactions for liquid Na2CO3-Na2S

1988-1990: Sangster & Pelton

Thermodynamic model of non-ideal liquid and solid
solutions of alkali salts without sulfide
Na+,K+//CO32-, SO42-, Cl-, OH-
 Thermodynamic modelling
Developments & Highlights (2)
1984present: Backman et al.
Thermodynamic model for the recovery boiler smelt
Na+,K+//S2-, S2O72-, CO32-, SO42-, Cl-, OH-
Equilibrium modeling of recovery boiler chemistry,
melting properties of superheater deposits,
pressurized black liquor gasification etc.

2000: Pelton, Chartrand and Eriksson

Modified Quasichemical Model in Quadruplet
Approximation
Thermodynamic model developed for complex
molten salts
Large amount of salt systems have been modelled
and multicomponent phase equilibrium is accurately
predicted
 Thermodynamic model for the
molten phase
New thermodynamic model - Modified Quasichemical
Formalism in the quadruplet approximation

Based on molten salt theory and takes into account

short-range ordering (on molecular level) in the liquid

Previous models for molten salts can be incorporated

previous optimized binary systems can be directly
incorporated

New components can easily be incorporated in the

model
Ca2+, Mg2+ , Heavy metals etc.
 Procedure for thermodynamic modelling

Evaluation of experimental thermodynamic data for

pure phases and experimental phase equilibrium data

Choice of thermodynamic model (mathematical

description) for the solution properties of solutions
(liquid, solid solutions, gas)

Optimization of solution interaction parameters and

unknown or uncertain thermodynamic data of pure
phases using experimental data as input

Calculation of phase equilibrium and comparison with

experimental equilibrium data (FactSageTM)
 Thermodynamic modelling

A good thermodynamic model/database for solids and

liquid should:
predict the phase equilibrium (=melting properties) of binary
and higher order systems within the uncertainties of
experimental investigations of these systems
give good predictions of the phase equilibrium for conditions
where no experimental data exist
NOTE! All experimentally determined melting data are
NOT equilibrium data
Examples of non-equilibrium phenomena:
Supercooling of liquids
Equilibration of solid solutions
Examples of modelled subsystems
relevant for the recovery boiler
 Recovery Boiler Smelt

The liquid phase in the char bed consists

mainly of Na2CO3, Na2S and Na2SO4, with
minor amounts of other K, Cl and S
species
Existence of polysulfides has been shown
to reduce the first-melting temperature
of the smelt
 Na2S - Na2CO3 Na2S - Na2SO4
1200

1100

1000
Liquid Liquid

Liquid + Na2S 900

T (C)
T (C)

800 Liquid+Na2S
Na2(CO3,S) (ss)

Na2(SO4,S)(ss)
700
600
Na2(CO3,S)(ss) + Na2S
Na2(SO4,S)(ss)+Na2S

400 500
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
x(Na2S) x(Na2S)

Na2CO3 - Na2SO4
900

880

Liquid
860
T (C)

840

820
Na2(CO3,SO4) (ss)

800
0.0 0.2 0.4 0.6 0.8 1.0
x(Na2CO3)
 Na2S-K2S-S
S
Two

0.9

0.1
liquids
254 C

0.8

0.2
0
20

0.7

0.3
300
400
0

0.6

0.4
30

475 C Na2S2 491 C

0
40
K2S2
0.5

0.5
500

70
0.4

0.6
0
0

800
60
0.3

0.7
900

0
70
0.2

0.8
1000

0
80
0.1

0.9
1100

0
90
Na2S 0.9 0.8 0.7 0.6 0.5
mole fraction
0.4 0.3 0.2 0.1
K2S

1175 C 948 C
 Na2S-K2S-S
S
Two Lowest melting

0.9

0.1
liquids
point 73 C

0.8

0.2
0
20

0.7

0.3
300
400
0

0.6

0.4
30
0
40
Na2S2 K2S2
0.5

0.5
500

70
0.4

0.6
0
0

800
60
0.3

0.7
900

0
70
0.2

0.8
1000

0
80
0.1

0.9
1100

0
90
Na2S 0.9 0.8 0.7 0.6 0.5
mole fraction
0.4 0.3 0.2 0.1
K2S
 Melting properties of carry-over
particles and superheater deposits
The liquid phase is of great importance
for deposit formation on superheaters
and for the corrosion of superheaters

Deposits are generally consist of

Na+,K+//SO42-,CO32-,Cl-,S2-

Acidic sulfates (S2O72-, HSO4-)may form in

boiler bank and economizers
Mixtures of NaCl, Na2SO4
and Na2CO3
 Na2SO4 - (0.35 Na2Cl2 + 0.65 Na2CO3)
900

Bergman et al. (1958)

800

Liquid
T(C)

700
Liquid+Na2(SO4,CO3)

600

bo Akademi, unpubl.
NaCl+Na2(SO4,CO3)
500
0.0 0.2 0.4 0.6 0.8 1.0
x(Na2SO4)
 Na2CO3 - (0.85 Na2SO4 + 0.15 Na2Cl2)
900

Bergman et al. (1958)

Liquid
800
T(C)

Liquid+Na2(SO4,CO3)
700

bo Akademi, unpubl.

600
0.0 0.2 0.4 0.6 0.8 1.0
x(Na2CO3)
Mixtures of Na+, K+/SO42-, Cl-

(NaCl, KCl, Na2SO4, K2SO4)

 Na2SO4-(KCl)2 Solidus, T0
900

800
T(C)

700

600

500
0.0 0.2 0.4 0.6 0.8 1.0
x(Na2SO4)
KCl Na2SO4
 Na2SO4-(KCl)2 Liquidus, T100
900

800
T(C)

700

600

500
0.0 0.2 0.4 0.6 0.8 1.0
x(Na2SO4)
KCl Na2SO4
Stability of alkali pyrosulfates
(Na2S2O7, K2S2O7)
 Na2SO4-Na2S2O7
p(O2) = 0.05 bar

-1
Liquid

-2 10000
log10(p(SO3)/bar)

ppm SO3
-3 Na2S2O7(s) Na2SO4(s) 1000

-4 2200 ppm SO3 100

-5
10

-6
200 300 400 500 600 700 800
T(C)
 K2SO4-K2S2O7
p(O2) = 0.05 bar

-1
Liquid
-2 10000
log10(p(SO3)/bar)

K2S2O7(s)

ppm SO3
-3 1000

-4 100
K2SO4(s)
-5 150 ppm SO3 10

-6
200 300 400 500 600 700 800
T(C)
 (Na,K)2SO4 - (Na,K)2S2O7
p(O2) = 0.05 bar, K/(Na+K)=0.1

-1

Liquid
-2 10000
log10(p(SO3)/bar)

ppm SO3
-3 1000

-4 100

-5
10
50 ppm SO3
-6
200 300 400 500 600 700 800
T(C)
 Summary

The melting behaviour of multicomponent alkali

salts in the recovery boiler has been modelled
using a new thermodynamic model for the
liquid phase

The thermodynamic model can reproduce most

experimental data of melting of the complex
salts within error limits