THERMOCHEMICAL MODELING OF

DIRECT CAUSTICIZATION OF BLACK

LIQUOR USING SODIUM TRI-TITANATE

Risto Pajarre, VTT Processes

Adriaan van Heiningen, University of Maine
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Outline

Thermodynamic equilibrium calculations using Gibbs free

energy minimization on a spreadsheet (ChemSheet)
Inclusion of chemical kinetics in ChemSheet
Black liquor gasification and direct causticization application
Description of constraining chemical kinetics
Computational results with/without recirculation of gasification
gas
Conclusions

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Chemical Equilibrium and Gibbs Free Energy

Minimization

The Gibbs free energy (G = ni i ) of a closed system

reaches its minimum value (for given pressure and
temperature) at equilibrium.
The equilibrium state can be solved as a non-linear
optimization problem where the chemical potentials are
typically supplied to the solver as known functions of
temperature, pressure and composition:

i = i0 + RT ln xi i
where
i = i (x j , T , p )

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Inclusion of kinetic constraints

In many important reaction systems the Initial inputs

effect of reaction kinetics can not be
ignored Free energy minimization t0 Min(G) (with kinetics frozen)
calculation can still be used to calculate
the effect of side reactions and various State t = t0
thermodynamic values such as heat
production, if the advancement of Reaction kinetic calculation
necessary reactions can be
constrained. t1 Min(G) (with kinetics frozen)

State t = t1
Necessary kinetic constraints to the
system can bet set as new Reaction kinetic calculation
components (= columns in the
stoichiometric matrix)
t2 Min(G) (with kinetics frozen)

State t = t2

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Black Liquor Gasification with Titanate Direct

Causticization

Major equilibrium reactions

CO + H2O CO2 + H2
2 CO C + CO2
Na2S + CO2 + H2O Na2CO3 + H2S
CO + 3 H2 CH4 + H2O

Kinetically controlled reactions

5 (Na2O3TiO2) + 7 Na2CO3 3 (4Na2O5TiO2) + 7 CO2
C + H2O CO + H2
C + CO2 2 CO
Na2SO4 + 4 C Na2S + 4 CO

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What Conditions for Kraft BLG with Titanate Direct

Causticization

Above 675 C to allow reasonable direct causticization

kinetics
Above 700 C to allow reasonable sulfate reduction
Use low pressure steam gasification to keep CO2 partial
pressure low ( 0.1 atm) for direct causticization

Medium temperature (700 750C) atmospheric gasification

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Inputs
Elemental Analysis of Black Liquid Solids (Gullichsen and Fogelholm, 2000):
Element S Na K Cl C H O N Inerts
w% 4.2 19.4 1.6 0.6 35 3.5 35.4 0.1 0.2

Calculated Chemical Species (based on 1 kg bls)

Potassium replaced by equimolar amount of sodium

21% of S as elemental sulfur to obtain experimental sulfur pyrolysis loss

All chlorine as NaCL

Remaining sodium as Na2CO3

Remaining oxygen as CO

Remaining carbon as elemental carbon

Hydrogen and nitrogen in elemental form

Na2SO4 NaCl Na2CO3 CO C H2 S N2 SiO2 Total

Mole 1.03 0.17 3.30 8.07 17.77 17.36 0.28 0.04 0.03 48.05
gram 147 9.9 350.2 226.1 213.2 35.0 8.8 1.0 2.0. 993.2

Additions: Steam (1.2mol/mol org. C) and Na2O*3TiO2(0.876kg/kgBLS)

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Simulation of Fast Pyrolysis of Black Liquor Solids

Comparison with Pyrolysis Yield Losses Measured by Jian Li (1989)

Jian Li used oxidized black liquor

No direct causticization, sulfur reduction or carbon gasification

Ratio of elemental S/Na2SO4 in bls chosen to obtain agreement with

sulfur loss obtained by Li.

Yield Loss (%) C O Na H S Overall weight

Jian Li 29 39 4.4 91 21 30
This work 28 36 0 100 21 28

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Reaction Kinetics
5(Na2O 3TiO2 ) + 7 Na2CO3 3(4 Na2O 5TiO2 ) + 7CO2 Causticization of Na2CO3
(
X = 1 (1 k1t ) X u
3
)
where
107720

X u = 0.9 and k1 = 626560e 8.31451*T(K)
1.035h 1 ( at 700o C )

C + CO2 / H 2O CO + CO / H 2 Carbon gasification

d [C ] 7 x1010 K 1 [CO2 ]e 30, 070 / T ( K ) 3 x10 9 K 3 [ H 2 O]e 25, 200 / T ( K ) mol
= + 3
dt [CO 2 ] + K 2 [CO ] [ H 2 O ] + K 4 [ H 2 ] m s
where
K1 = K 3 = min([Na ], [C ]), K 2 = 3.4, K 4 = 1.42

Sodium sulfate reduction

4C + Na 2 SO4 = Na 2 S + 4CO
d [Na 2 SO 4] mol
= 2k 2 t [Na SO ] e (kt )
2

2 4 0 3
dt m s
where
k = 1.7 1012 e 35010 T
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C H O N Ti S Na Cl Si Ar R(C) R(Na2CO3) R(Na2SO4)
Ar(g) 1
CH4(g) 1 4
CO(g) 1 1
CO2(g) 1 3
Cl2(g) 3
H2(g) 2
H2O(g) 2 1
H2S(g) 2 1
HCN(g) 1 1 1
HCl(g) 1 1
gasN2(g) 2
NH3(g) 3 1
NO(g) 1 1
NO2(g) 2 1
Na(g) 1
NaCN(g) 1 1 1
NaOH(g) 1 1 1
O2(g) 2
S(g) 1
S2(g) 2
SO2(g) 2 1
*4Na2O*5TiO2 14 5 8
C 1 1
Na2CO3 1 3 2 1
Na2O 1 2
Na2O*3TiO2 7 3 2
Na2S 1 2
Na2SO4 4 1 2 1
NaCl 1 1
NaOH 1 1 1
SiO2 2
Ti 1
R_C+ 1
R_C- -1
R_Na2CO3+ 1
R_Na2CO3- -1
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R_Na2SO4+ 1
R_Na2SO4- -1
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Batch/Plug Flow Simulation Results

Gas Composition versus Time

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Batch/Plug Flow Simulation Results

Gas Composition versus Time (Logarithmic scale)

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Batch/Plug Flow Simulation Results

Solids Composition versus Time (Logarithmic scale)

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Batch/Plug Flow Simulation Results

Reaction Rates versus Time

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Batch/Plug Flow Simulation Results

Reaction Rates versus Time

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Batch/Plug Flow Simulation Results

Effect of Product Gas Recirculation (10% of total steam flow)

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Batch/Plug Flow Simulation Results

Effect of Product Gas Recirculation (10% of total steam flow)

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Batch/Plug Flow Simulation Results

Effect of Product Gas Recirculation (10% of total steam flow)

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Conclusions

Inclusion of Reaction Kinetics in Gibbs Energy Minimization

calculation is a powerful tool for industrial process simulation

Complete direct causticization within one hour

Final carbon burnout by carbothermic sulfate reduction

Carbon gasification limited by high CO concentration

Gas recycle decreases carbon consumption by gasification

sothat more carbon is available for sulfate reduction

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