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TEKNISKA

FAKULTETEN

Processkemiska Centret

ÅBO AKADEMI

FACULTY OF TECHNOLOGY

Process Chemistry Centre

REPORT 07-03

Thermochemistry and melting properties of alkali salt mixtures in black liquor conversion processes

Daniel Lindberg

mixtures in black liquor conversion processes Daniel Lindberg Academic Dissertation Laboratory of Inorganic Chemistry

Academic Dissertation

Laboratory of Inorganic Chemistry

Thermochemistry and melting properties of alkali salt mixtures in black liquor conversion processes

Daniel Lindberg

in black liquor conversion processes Daniel Lindberg Academic dissertation Åbo Akademi University Faculty of

Academic dissertation

Åbo Akademi University Faculty of Technology

Process Chemistry Centre Laboratory of Inorganic Chemistry

Preface

Preface

The work described in this thesis was carried out at the Process Chemistry Centre at Åbo Akademi University from 2002 to 2007 and at CRCT, École Polytechnique de Montréal during a six month stay in 2004. Funding for the work has been received from several sources: Nordic Graduate School of Biofuel Science and Technology, part of the Nordic Energy Research, the Fondation de l’École Polytechnique de Montréal, U.S. Borax Inc., Andritz Oy, Foster Wheeler Energia Oy, International Paper Inc., Kvaerner Power Oy, Oy Metsä Botnia Ab, Vattenfall Utveckling AB and the National Technology Agency of Finland (TEKES). All financial support is gratefully acknowledged.

Professor Rainer Backman has been the main supervisor of the work presented in this thesis. I wish to express my deepest gratitude to Rainer for giving me the opportunity to do research on interesting topics in the field of high-temperature inorganic chemistry. The endless hours we have spent discussing thermodynamics, chemistry, and science in general have always kept me inspired to push forward in my research. I especially appreciate that he has always been available to help and support me in my work.

The thermodynamic modeling presented in publications III-VI was performed together with Professor Patrice Chartrand at CRCT, École Polytechnique, in Montréal, Canada. The modeling work was planned in cooperation with Professor Chartrand, and he functioned as my supervisor during my visits to Montréal. I wish to thank Patrice for giving me the opportunity to visit CRCT, Montréal and for his supervision during my stays there. Patrice’s dedication to my work has helped me tremendously, and for that I am greatly thankful. I also want to acknowledge all the people at CRCT for making my stays in Canada enjoyable.

I want to express my gratitude to Professor Mikko Hupa for giving me the opportunity to do my doctoral studies at the Laboratory of Inorganic Chemistry. His competence and his positive attitude have been a source of inspiration and it has given me a great platform for my doctoral studies.

Special thanks go to Mr. Linus Perander for performing the experimental work for Publication II, as well as being a co-author of the paper. In addition, Linus’ comments on

Preface

Publications III-VI were valuable. His contribution to the doctoral study has been important, and his cooperation and friendship are greatly appreciated.

I thank Dr. Saied Kochesfahani and Dr. Helen Rickards for their support on the borate

autocausticizing work, and for their contributions as co-authors to Publication II. Dr. Nikolai DeMartini and Professor Chris Bale are acknowledged for their comments on publications related to the thesis, and in addition Mrs. Debby Repka for her comments on the thesis.

Mr. Peter Backman performed the experimental work for Publications I and VI. I wish to thank him for his diligence and accuracy in the experimental work.

I want to thank all my colleagues, both past and present, at the Laboratory of Inorganic

Chemistry who have ensured that my doctoral studies have been a tremendously rewarding time. I especially want to acknowledge Dr. Mischa Theis and Mr. Johan Werkelin, with whom I have shared the joy and agony of making a doctoral thesis the last couple of years.

Finally, I want to thank all my friends and my family, whose love and support have kept my spirits up high during the whole process of making a doctoral thesis. I am especially grateful to my parents, whose support and encouragement have made it possible for me to to pursue a career in the field of science.

Åbo, February 2007

Daniel Lindberg

Abstract

Abstract

Alkali salt mixtures play an important role in the chemical processes in a kraft recovery boiler burning black liquor. The smelt, a liquid phase containing mainly Na 2 CO 3 and Na 2 S, is the main chemical product from the recovery boiler and is utilized for producing the pulping chemicals. Several reactions occur in the smelt, such as the sulfur reduction, which is a reaction between the smelt and the char carbon. Alkali compounds, such as alkali chlorides and various sulfur-containing species, play an important role in the formation of deposits on heat exchanger surfaces in the boiler. Molten alkali salts can also cause corrosion problems in the boiler. The thermochemistry and melting properties of alkali salt mixtures involved in black liquor and biomass combustion have been studied by evaluating and optimizing the thermodynamic data for all known phases in the Na + ,K + /CO 3 2- ,SO 4 2- ,S 2- ,S 2 O 7 2- ,S x 2- ,Cl - , Va - system using experimental data as input. Additional experimental data for melting temperatures in the ternary NaCl-Na 2 CO 3 -Na 2 SO 4 and KCl-K 2 CO 3 -K 2 SO 4 systems were obtained by simultaneous differential thermal analysis and thermogravimetry and the results were used as input for the thermodynamic optimization. The thermodynamic properties of the liquid phase were modeled using the Modified Quasichemical Model in the Quadruplet Approximation, which is a thermodynamic model developed especially for molten salts. The obtained thermodynamic database reproduces the solid-liquid equilibrium of the binary, ternary and quaternary systems within the experimental uncertainties. The database of thermodynamic data for all phases can be used in Gibbs energy minimization software for calculating the phase equilibria and all thermodynamic properties of multicomponent alkaline salt mixtures. The alkali salts are of great importance for ash-related problems in biomass combustion and for processes in black liquor combustion. Predictions of the melting behavior of the alkali salts are useful for understanding the behavior of the smelt bed and the formation of harmful deposits in the kraft recovery boiler. Borate autocausticizing is a concept for reducing the lime consumption at pulp mills by adding boron to the pulping process. The amount of Na 2 CO 3 that needs to be causticized for the production of white liquor can be reduced by the borate reactions in

Abstract

the kraft recovery boiler. The autocausticizing reactions mainly occur in the smelt or in burning black liquor droplets. The effects of chemical and physical variations on the borate autocausticizing reactions in mixtures of alkali carbonates and alkali borates were studied by simultaneous differential thermal analysis and thermogravimetry. The results showed that the borate autocausticizing reactions are reversible, and that high temperatures and low borate contents enhance the conversion of borates to the preferred orthoborate form. High potassium contents and high partial pressures of CO 2 inhibit the autocausticizing reaction. High conversion of the autocausticizing reaction can be attained at the conditions prevalent in the char bed of a kraft recovery boiler. The experimental results can be used as input for future thermodynamic evaluations of borate-containing alkali salt systems involved in combustion of boron-containing black liquors.

Svensk sammanfattning

Svensk sammanfattning

Alkalisaltblandningar spelar en viktig roll i de kemiska processerna i en sodapanna. Sodapannesmältan, som huvudsakligen består av Na 2 CO 3 och Na 2 S, tappas ut ur sodapannan och används till att producera vitlut. Flera viktiga kemiska reaktioner sker i smältan. Svavelreduktionen sker huvudsakligen genom en reaktion mellan smälta och koks. Alkaliföreningar, till exempel alkaliklorider och olika alkali-svavel föreningar, kan leda till uppkomsten av beläggningar på värmeväxlarytor. Alkalisaltsmältor kan förorsaka korrosionsproblem i sodapannan. I denna studie har de termokemiska egenskaperna och smältbeteendet för alkalisaltblandningar relevanta för svartluts- och biomasseförbränning undersökts genom en evaluering av experimentella termodynamiska data och fasjämviktsdata för alla kända faser i det kemiska systemet Na + ,K + /CO 3 2- ,SO 4 2- ,S 2- ,S 2 O 7 2- ,S x 2- ,Cl - ,Va - . En termodynamisk optimering av de termodynamiska funktionerna för dessa faser utfördes på basen av evalueringen. Smälttemperaturerna för de ternära systemen NaCl-Na 2 CO 3 - Na 2 SO 4 och KCl-K 2 CO 3 -K 2 SO 4 undersöktes med simultan differentiell termisk analys och termogravimetri och resultaten utnyttjades som ingångsdata för den termodynamiska evalueringen. Smältfasens termodynamiska egenskaper modellerades med den modifierade kvasikemiska modellen, en termodynamisk modell utvecklad för jonsmältor. Jämviktsberäkningar med den erhållna termodynamiska databasen återger fastfas- vätskefasjämvikten för de undersökta binära, ternära och kvaternära systemen inom den experimentella osäkerheten. Databasen kan utnyttjas i program för kemiska jämviktsberäkningar baserade på minimering av Gibbs energi för att bestämma fasjämvikter och termodynamiska egenskaper för system av alkalisalter viktiga för askrelaterade problem i biomass- och svartlutsförbränning. Smältbeteendet hos alkalisalter ger information om förhållanden i smältbädden och om hur skadliga beläggningar uppkommer i sodapannan. Boratautokausticering är en metod ämnad att reducera kalkförbrukningen vid pappersmassabruk genom att tillsätta grundämnet bor i massaprocessen. Mängden Na 2 CO 3 som bör kausticeras för produktionen av vitlut kan minskas genom boratets

Svensk sammanfattning

reaktioner i sodapannan. Autokausticeringsreaktionerna sker huvudsakligen i smältan eller i brinnande svartlutsdroppar. Effekten av olika kemiska komponenter och fysikaliska förhållanden på autokausticeringsreaktionerna i blandningar av alkalikarbonater och alkaliborater undersöktes med simultan differentiell termisk analys och termogravimetri. Resultaten visade att boratautokausticeringsreaktionerna är reversibla och att höga temperaturer och låga boratkoncentrationer gynnar omvandlingen av boraterna till ortoborat, som är gynnsamt för autokausticeringen. Höga kaliumkoncentrationer och högt partialtryck av CO 2 hämmar autokausticeringsreaktionen. En hög omvandlingsgrad av boraterna kan uppnås vid förhållanden som råder i koksbädden i en sodapanna. De erhållna experimentella resultaten kan användas som ingångsdata för framtida termodynamisk evalueringar av alkaliboratblandningars kemi vid användning av bor för att befrämja autokausticering vid svartlutsförbränning.

Table of contents

Table of contents

Preface

i

Abstract

iii

Svensk sammanfattning

v

Table of contents

vii

List of publications

x

1. Introduction

1

1.1

Objective of the study

4

2. Alkali salts in the recovery boiler

5

3. Thermodynamic modeling of alkali salt mixtures involved in black liquor combustion 9

3.1 Overview of the properties of ionic compounds and solutions

9

3.2 Thermodynamic equilibrium modeling

10

3.3 Optimization of phase diagrams and thermodynamic data

12

3.4 Thermodynamic models of ionic solutions

13

3.4.1 Ideal solutions

 

13

3.4.2 Nonideal solutions

14

3.4.3 Sublattice models

 

16

3.4.4 Compound Energy Formalism

18

3.4.5 Modified Quasichemical Model in the Quadruplet Approximation

19

3.4.6 Extrapolation of excess Gibbs energy in multicomponent solutions

25

3.5

Thermodynamic evaluation and optimization of the Na + , K + /CO 3 2- , SO 4 2- , S 2- ,

S 2 O 7 2- , S x 2- , Cl - , Va - system

27

3.5.1

The Na-K-S system

29

3.5.1.1 Na-S

 

31

3.5.1.2 K-S

33

3.5.1.3 Na-K

33

3.5.1.4 Na

2 S-K

2 S

34

3.5.1.5 Na 2 S-K 2 S-S

34

Table of contents

3.5.2 The Na + ,K + /CO 3 2- ,SO 4 2- ,Cl - ,S 2- ,S 2 O 7 2- system

3.5.2.1 Binary systems

3.5.2.2 Na 2 CO 3 -Na 2 SO 4

3.5.2.3 Na 2 CO 3 -Na 2 S

3.5.2.4 Na 2 SO 4 -Na 2 S

3.5.2.5 Na 2 SO 4 -Na 2 S 2 O 7

3.5.2.6 NaCl-Na 2 SO 4

3.5.2.7 NaCl-Na 2 CO 3

3.5.2.8 NaCl-Na 2 S

3.5.2.9 K 2 CO 3 -K 2 SO 4

3.5.2.10 K 2 CO 3 -K 2 S

3.5.2.11 K 2 SO 4 -K 2 S

3.5.2.12 K 2 SO 4 -K 2 S 2 O 7

3.5.2.13 KCl-K 2 SO 4

3.5.2.14 KCl-K 2 CO 3

3.5.2.15 Na 2 CO 3 -K 2 CO 3

3.5.2.16 Na 2 SO 4 -K 2 SO 4

3.5.2.17 Na 2 S 2 O 7 -K 2 S 2 O 7

3.5.2.18 NaCl-KCl

3.5.2.19 Ternary systems

3.5.2.20 Na 2 CO 3 -Na 2 SO 4 -Na 2 S

3.5.2.21 NaCl-Na 2 CO 3 -Na 2 S

3.5.2.22 NaCl-Na 2 CO 3 -Na 2 SO 4

3.5.2.23 KCl-K 2 SO 4 -K 2 CO 3

3.5.2.24 Na 2 SO 4 -K 2 SO 4 -Na 2 S 2 O 7 -K 2 S 2 O 7

3.5.2.25 Na 2 CO 3 -Na 2 SO 4 -K 2 CO 3 -K 2 SO 4

3.5.2.26 NaCl-Na 2 SO 4 -KCl-K 2 SO 4

3.5.2.27 NaCl-Na 2 CO 3 -KCl-K 2 CO 3

36

36

38

38

38

39

41

41

42

43

44

45

46

47

47

49

50

50

51

52

53

54

55

57

59

61

63

64

Table of contents

3.5.3.28 Multicomponent systems: NaCl-Na 2 SO 4 -Na 2 CO 3 -KCl-K 2 SO 4 -K 2 CO 3 . 66

3.6 Discussion

68

3.7 Conclusions

68

4. Alkali borates in the kraft recovery boiler

69

4.1 Definitions of nonconventional causticizing concepts

70

4.2 Borate autocausticizing

71

4.2.1

Partial borate autocausticizing

74

4.3

Objective of the experimental study of borate autocausticizing

76

4.4.1

Borates in the recovery boiler

76

4.4.1.1 Alkali orthoborates

78

4.4.1.2 Alkali diborates

78

4.4.1.3 Alkali metaborates

79

4.4.1.4 Molten alkali borates

79

4.5 Experimental setup

82

4.6 Results

84

4.7 Discussion

90

4.8 Conclusions

92

5. Conclusions and implications

93

References Appendix A: Thermodynamic data of pure compounds Appendix B: Thermodynamic functions of solid solutions Appendix C: Interaction parameters of the liquid phase

95

List of publications

List of publications

I. Lindberg, D., Backman, R. (2004) Effect of temperature and boron contents on the autocausticizing reactions in sodium carbonate/borate mixtures. Industrial and Engineering Chemistry Research, 2004, 43, 6285-6291.

II. Lindberg, D., Perander, L., Backman, R., Hupa, M., Kochesfahani, S., Rickards, H. (2005) Borate autocausticizing equilibria in recovery boiler smelt. Nordic Pulp and Paper Research Journal, 2005, 20(2), 232-236.

III. Lindberg, D., Backman, R., Hupa, M., Chartrand, P. (2006) Thermodynamic evaluation and optimization of the (Na+K+S) system. The Journal of Chemical Thermodynamics, 2006, 38(7), 900-915.

IV. Lindberg, D., Backman, R., Chartrand, P. (2006) Thermodynamic evaluation and optimization of the (Na 2 SO 4 +K 2 SO 4 +Na 2 S 2 O 7 +K 2 S 2 O 7 ) system. The Journal of Chemical Thermodynamics, 2006, 38(12), 1568-1583

V. Lindberg, D., Backman, R., Chartrand, P. Thermodynamic evaluation and optimization of the (Na 2 CO 3 +Na 2 SO 4 +Na 2 S+K 2 CO 3 +K 2 SO 4 +K 2 S) system. The Journal of Chemical Thermodynamics, In Press

VI. Lindberg, D., Backman, R., Chartrand, P. Thermodynamic evaluation and optimization of the (NaCl+ Na 2 SO 4 +Na 2 CO 3 +KCl+K 2 SO 4 +K 2 CO 3 ) system. The Journal of Chemical Thermodynamics, In Press

Chapter 1- Introduction

1. Introduction

The kraft pulping process is the main chemical pulping process in the world today. In contrast to the mechanical pulping processes, chemical pulping processes separate the cellulose from wood chips by chemical means,. In the kraft pulping process, the wood chips are cooked in an alkaline solution containing dissolved Na 2 S and NaOH. Lignin and some carbohydrate material are dissolved from the wood chips during cooking. The resulting pulp, which is made up mainly of wood fibers, is separated from the cooking solution and used for the production of different pulp and paper products. The spent cooking solution, which is called black liquor, contains the dissolved organic matter, the inorganic material from the wood, and the spent cooking chemicals. The processing of the black liquor is an integral part of pulp mill operations. Much of the water has to be evaporated from the black liquor so that it can be burned. The concentrated black liquor is combusted in the kraft recovery boiler to produce heat and power and to convert the inorganic substances into regenerable forms. Sodium and sulfur compounds are converted under reducing conditions into a liquid phase called the smelt, consisting of Na 2 CO 3 and Na 2 S. The smelt flows from the furnace floor to a dissolving tank for further processing where the alkaline cooking solution is recovered. A schematic diagram of the processes and streams in the chemical recovery cycle of a typical kraft pulp mill is shown in Figure 1.1.

Chapter 1- Introduction

CHIPS

H 2 O PULP Paper Pulping Washing FIBRES mill Weak black liquor WHITE LIQUOR Evaporators
H 2 O
PULP
Paper
Pulping
Washing
FIBRES
mill
Weak black liquor
WHITE
LIQUOR
Evaporators
H
2 O
Black liquor
Flue gases
Recovery
Steam
boiler
Electricity
Smelt
Dissolver
Flue gases
Green liquor
Lime mud
Causticising
Lime kiln

Lime

Figure 1.1. Schematic diagram of chemical recovery in the kraft pulping process

The dual role of the kraft recovery boiler as both a chemical reactor and a heat/power boiler presents unique challenges compared to traditional heat and power boilers. Not only should the heat be recovered and emissions kept low, but also a chemical product of the desired quality should be produced. The fuel, black liquor, adds to the complexity of the processes in the kraft recovery boiler, because it contains large amounts of sodium and sulfur originating from the cooking chemicals. This gives it unusual combustion properties compared to other fuels, which can lead to serious problems with fouling, plugging, and corrosion in the recovery boiler. In many of the processes in the kraft recovery boiler, the role of inorganic alkali compounds is central. The main reaction related to chemical recovery in the boiler, the reduction of sulfur to the preferred sulfide species S 2- , involves reactions between char carbon and molten sodium compounds containing sulfurous anions [1]. In addition, organically associated sodium plays an important catalytic role in the conversion of the

Chapter 1- Introduction

char carbon [2-4]. In some of the more problematic aspects of operations in the recovery boiler, like fouling, plugging, and corrosion, the role of molten salts is significant. The behavior of molten salts is also of great interest when developing new technologies or concepts for chemical recovery from black liquor. In the direct causticizing or autocausticizing concepts, chemicals are added to or are present in the chemical recovery cycle in order to decrease the load on the causticizing units of the pulp mill. Many of the important reactions involved occur in the liquid phase in the recovery boiler [5]. The chemical behavior of the various alkali compounds and their mixtures is of utmost importance for processes occurring in the kraft recovery boiler and other similar devices. Several approaches are required to investigate the behavior of the alkali compounds and their mixtures in the kraft recovery boiler, and to predict how they affect the processes. Experimental studies are the basis for understanding the chemical processes in the recovery boiler. Data on the chemical equilibrium of reactions, rates of reactions, and mass transfer of the different phases and species are needed to understand the chemical reactions in the kraft recovery boiler. However, in the study of complex chemical processes, such as the combustion of black liquor and the reactions related to chemical recovery occurring on such a large scale, the need for proper modeling tools arises. Thermodynamic modeling gives the equilibrium composition of phases and species under specified conditions, while chemical kinetics modeling takes into account the temporal variation of the chemical reactions. Additional models for diffusion in particles and for fluid flow are essential, as thermodynamic modeling does not consider how particles come into contact with each other, which is important when chemical reactions involve two or more reactants. To obtain a comprehensive understanding of the chemistry in the kraft recovery boiler requires all the above-mentioned modeling approaches plus other models. Computational fluid dynamics (CFD) can be used to construct comprehensive models of the processes in the kraft recovery boiler, but the validity of such simulations is dependent on the various submodels that are used. Thermodynamic modeling is often used to predict the melting properties of the inorganic condensed phases in the boiler; it is based on Gibbs energy minimization techniques, assuming that the Gibbs energy of all phases is known. For the thermodynamic modeling to be a useful and accurate tool, it is essential to have a

Chapter 1- Introduction

consistent set of thermodynamic data for all phases. The thermodynamic data for solution phases must also be modeled, which requires the choice of appropriate solution models. The Calphad method is a procedure to evaluate the phase equilibrium and thermodynamic data and to optimize the Gibbs energy functions of the phases involved. With an appropriate description of the thermodynamic properties of the alkali salt mixtures, several important phenomena in the kraft recovery boiler can be modeled and understood, such as melting of the recovery boiler smelt and superheater deposits, sulfur reduction reactions, autocaustizing reactions, and volatilization of alkali compounds.

1.1 Objective of the study

The objective of the present study was to gain a better understanding of the reactions and phase relations of alkali salts in the kraft recovery process. The thermodynamic properties of the alkali salt mixtures typically found in the kraft recovery boiler, mainly sodium and sulfur-containing salts, were evaluated and optimized based on experimental data from the literature to obtain a consistent thermodynamic database. The database can be used to model and shed light on phenomena occurring in the kraft recovery boiler, such as smelt bed behavior, deposit formation and corrosion. The main emphasis was on the solid-liquid equilibrium of alkali salt mixtures, but the solid phase equilibrium and the solid-liquid-gas equilibrium were also studied. Additional experiments were conducted for ternary systems to produce new input data for the thermodynamic evaluation. In addition, an experimental study was carried out on the reactions of borates in alkali salt mixtures to understand the effect of chemical components and physical conditions on the borate autocausticizing concept. The results can be used as input for future thermodynamic evaluations of alkali borate mixtures, which play an important role in the combustion of boron-containing black liquors.

Chapter 2-Alkali salts in the recovery boiler

2. Alkali salts in the recovery boiler

Black liquor is a complex material consisting of water, organic residues from pulping,

and dissolved or solid inorganic compounds. The specific properties and composition of

black liquor are dependent on the raw material and the processes used by the pulp mill.

The primary organic compounds are lignin, polysaccharides, carboxylic acids and

extractives. The inorganic compounds are alkali salts such as Na 2 CO 3 , Na 2 S, Na 2 S 2 O 3 ,

Na 2 SO 3 , Na 2 SO 4 , NaCl, NaOH, NaHS, Na 2 S x , and corresponding potassium compounds

[6]. These salts may be solid or dissolved, depending on the water content of the black

liquor. A large part of the sodium and sulfur that forms inorganic salts in the recovery

boiler exists in organic compounds in the black liquor. The speciation of the elements in

the black liquor is dependent on the pulp mill processes and can vary considerably within

a pulp mill and between different mills. The elemental composition of typical

Scandinavian and North American virgin black liquors is given in Table 2.1. The main

difference between the elemental composition of black liquor and that of solid fuels such

as coal, wood, and straw, is the higher concentration of sodium and sulfur. Black liquor

has unique characteristics as a fuel due to its high water content and the high inorganic

material content, which give it low heating values compared to other fuels.

Table 2.1. Typical elemental composition (in wt-%) of black liquor from softwood and hardwood black liquors from Scandinavia and North America on a dry solid basis [6].

 

Scandinavian wood

 

North American wood

 

Element

Softwood (pine)

Hardwood (birch)

Softwood (pine)

Hardwood

Typical

Range

Typical

Range

Typical

Range

Typical

Range

Carbon, %

35.0

32-37

32.5

31-35

35.0

32-37.5

34.0

31-36.5

Hydrogen, %

3.6

3.2-3.7

3.3

3.2-3.5

3.5

3.4-4.3

3.4

2.9-3.8

Nitrogen, %

0.1

0.06-0.12

0.2

0.14-0.2

0.1

0.06-0.12

0.2

0.14-0.2

Oxygen, %

33.9

33-36

35.5

33-37

35.4

32-38

35.0

33-39

Sodium, %

19.0

18-22

19.8

18-22

19.4

17.3-22.4

20.0

18-23

Potassium, %

2.2

1.5-2.5

2.0

1.5-2.5

1.6

0.3-3.7

2.0

1-4.7

Sulfur, %

5.5

4-7

6.0

4-7

4.2

2.9-5.2

4.3

3.2-5.2

Chlorine, %

0.5

0.1-0.8

0.5

0.1-0.8

0.6

0.1-3.3

0.6

0.1-3.3

Others, %

0.2

0.1-0.3

0.2

0.1-0.3

0.2

0.1-2.0

0.5

0.1-2.0

Chapter 2-Alkali salts in the recovery boiler

The main purpose of the combustion of black liquor is to produce heat, which can be recovered and utilized for other processes; it also provides energy for the conversion of inorganic compounds into the smelt, which is recovered and processed into the cooking chemicals for the pulping process. Black liquor, which has been dried to a dry solid content of 70-85%, is sprayed as droplets into the recovery boiler furnace. Combustion occurs in several stages: As black liquor droplets enter the furnace, they are dried and water vapor is released. Next, they are heated and gas components with low molecular weights, such as CO, CO 2 , CH 4 , H 2 and H 2 S, are released in the pyrolysis or devolatilization stage [7]. The devolatilization stage is usually associated with a considerable increase in the black liquor droplet volume. The combustible gases are burned when they come into contact with oxygen. Finally, the solid char matrix begins reacting with oxygen. Much of the inorganic matter remains in the char, and during the char carbon conversion, the important sulfur reduction reactions occur. The overall reduction reaction can be described by the following equation:

Na 2 SO 4 (l) + 2(1+X) C(s) Na 2 S(l) + 2(1-X) CO 2 (g) + 4X CO(g), [0 X 1]. [Eq. 2.1]

The reduction of sulfate to sulfide is an endothermic process, and the energy required for the reaction is provided by the heat released when the char carbon burns. Organically associated sodium plays an important catalytic role in the conversion of the char carbon [2-4]. As the char carbon burns away, the remaining molten salt coalesces and forms the smelt. If the smelt comes into contact with oxygen, the sulfide can be re-oxidized according to the following reaction:

Na 2 S(l) + 2 O 2 (g) Na 2 SO 4 (l)

[Eq. 2.2]

In reality all the different stages of black liquor droplet combustion overlap [8, 9]. Ideally, in the recovery boiler, the drying and the devolatilization steps take place in flight before the droplets reach the char bed at the bottom of the furnace. Char

Chapter 2-Alkali salts in the recovery boiler

combustion and sulfur reduction take place on the char bed, and the smelt containing Na 2 S and Na 2 CO 3 , is removed from the recovery boiler before re-oxidation occurs. In addition to the combustion of black liquor and the sulfur reduction, there are other processes involving alkali compounds that are important for the operations of the recovery boiler. The volatilization and condensation of alkali salts play an important role in the formation of so-called fume, which can cause unwanted deposit buildup on heat exchangers. Also, Na 2 CO 3 can react with carbon, producing sodium vapor, CO, and CO 2 in the recovery boiler [10]. The overall reaction is given by Equation 2.3:

Na 2 CO 3 (s,l) + X C(s) 2 Na(g) + (2X-1) CO(g) + (2-X) CO 2 (g) [0.5X2].

[Eq. 2.3]

The formation of gaseous Na-compounds is enhanced by the higher furnace temperatures achieved by lowering the water content of the black liquor. The condensation of the alkali vapors is related to fume formation in the boiler, which can cause deposit buildup on heat exchangers. The fume particles generally have a diameter of about 0.1 to 1 μm [11]. In modern boilers, which burn black liquor with a high dry solids content, SO 2 emissions are very low because SO 2 reacts with gaseous Na-compounds to form condensed Na 2 SO 4 , which makes up a large part of the fume particles. Moreover, NaCl and KCl are also enriched in the fume because the chlorides have higher volatility than the other alkali compounds in the boiler. The formation of alkali salt deposits on heat exchanger surfaces is also related to the formation of carryover particles. Carryover particles are black liquor droplets or fragments of burning droplets that are mechanically entrained by the furnace gases. The size of carryover particles varies between 20 μm and 3 mm [11]. Their composition is similar to that of oxidized smelt, as the particles originate from entrained smelt or black liquor particles. However, mature carryover deposits generally have higher sulfate concentration due to sulfation of carbonates and/or chlorides. The deposits in the kraft recovery boiler are mixtures of fume particles and carryover particles in a ratio which varies in different parts of the boiler. Corrosion in the recovery boiler is often related to the presence of molten alkali salts. The existence of low-melting sodium polysulfides (Na 2 S n , n>1) in the char bed has

Chapter 2-Alkali salts in the recovery boiler

been suggested by Backman et al. [12] as a source of furnace floor corrosion. The alkali polysulfides melt at considerably lower temperatures than a mixture of Na 2 CO 3 , Na 2 SO 4 , and Na 2 S. Generally, the floor temperatures are kept below the melting temperatures of the smelt. However, the existence of a liquid phase in contact with the furnace floor may cause corrosion of the floor material at low temperatures. Corrosion of superheaters is often attributed to molten salt corrosion [13]; a liquid phase in the deposits is the corrosive agent. High concentrations of chlorides in the deposits usually give low first- melting temperatures and are often related to increased corrosion of the superheaters. However, the mechanisms of chlorine-induced corrosion are not fully understood. Formation of low-melting acidic sulfates, such as alkali disulfates (Na 2 S 2 O 7 , K 2 S 2 O 7 ) and alkali hydrogen sulfates (NaHSO 4 , KHSO4), are also related to corrosion in recovery boilers burning black liquors with high sulfur contents [14]. Alkali borate compounds also play an important role in the autocaustizing concept in recovery boilers firing borate-containing liquors. The behavior of alkali borates is discussed in detail in Section 4.

Chapter 3-Thermodynamic modeling

3. Thermodynamic modeling of alkali salt mixtures involved in black liquor combustion

3.1 Overview of the properties of ionic compounds and solutions

The solid and liquid alkali compounds in a kraft recovery boiler are ionic compounds. The solid sodium and potassium compounds, such as Na 2 SO 4 , Na 2 CO 3 and KCl, are often called salts. The term “salt” has traditionally been used for table salt or rock salt (NaCl) and for the ionic solid product that is formed when a metal hydroxide or oxide (base) reacts with an acid. The term “molten salt” is commonly used both in industry and in the scientific community to describe high-temperature ionic liquid phases. The term “ionic liquid” is mainly used for low or room temperature liquids of an ionic nature. Ionic compounds consist of electrically charged components, anions and cations, which are attracted to or repelled by each other due to Coulomb forces. The result is that ionic crystals have strong ordering, in which anions are surrounded by cations and cations are surrounded by anions in the crystal lattice. The anions reside on an anionic sublattice, with cations as the nearest neighboring ions, and vice versa for the cations. Ionic compounds usually have low volatility and high melting temperatures (except for room temperature ionic liquids), and in the liquid state, they are electrically conductive due to the mobility of the ions. In the liquid state, the ions are also arranged with anions surrounded by cations, and vice versa. Due to their mobility in the liquid state, the ions are not restricted to fixed lattice sites, but for modeling purposes quasi-sublattices for the anions and cations are used to describe the thermodynamic properties of ionic liquid phases [15-18]. Ionic melts have great importance in many industrial fields. In the manufacture of aluminum, molten cryolite (Na 3 AlF 6 ) is the base solvent for Al 2 O 3 in Hall-Héroult electrolysis cells [19]. Molten alkali and alkaline earth chloride mixtures are used as electrolytes in the production of metallic sodium and magnesium, where the corresponding chloride is electrolyzed to the metallic form, and the other chloride salts act as fluxes to lower the melting temperature of the mixture [19]. In the molten

Chapter 3-Thermodynamic modeling

carbonate fuel cell (MCFC) and the sodium-sulfur battery [20], which have been developed for medium-scale electricity production, ionic melts play an important role in the electrochemical reactions. The molten salt reactor (MSR) [21] is considered to be a promising type of nuclear reactor belonging to the class known as generation IV reactors. In this type of reactor, the fuel is uranium or plutonium fluorides dissolved in a molten mixture of NaF and ZrF 4 . Silicate melts, which consist of polymeric ionic species, are used for example in glass manufacturing. Ionic melts play an important role in chemical reaction engineering. In the production of sulfuric acid, a molten mixture of alkali disulfates and V 2 O 5 is the catalyst for the oxidation reaction of SO 2 to SO 3 in the contact process [19]. Low temperature or room temperature ionic liquids, which are molten organic salts, are becoming increasingly important as solvents and catalysts in chemical reaction engineering because of their thermal stability, low volatility, and ability to dissolve different types of chemical substances. The ionic species in ionic liquids are usually much more complicated than those in many inorganic salts, and the ionic liquids can be tailor-made for the specific purposes. The production of smelt in kraft pulping is one of the largest molten salt producing chemical processes today. About 200 million tons of black liquor dry solids are produced annually worldwide [22], and roughly one third of the mass is transformed into smelt, which is used for the production of pulping chemicals

3.2 Thermodynamic equilibrium modeling

In order to predict the chemical behavior of multicomponent multiphase systems, computational methods are needed to calculate the chemical equilibrium, the reaction kinetics, and the transport properties of the species of interest. This becomes very complicated for systems involving solid phases, a liquid phase, and a gas phase, especially if the chemical composition of the phases varies. The mathematical models need experimental data as input for the model parameters. Unfortunately for many

Chapter 3-Thermodynamic modeling

complex systems, these data do not exist or experimental results are too complicated to use for extracting model parameters. Therefore, a good description of the chemical behavior in simplified systems is essential for making predictions in more complicated systems. Thermodynamic modeling is a commonly used tool for predicting the chemical behavior of complex systems. It is often based on minimization of the Gibbs energy of the system, which can be calculated using modern software if thermodynamic data exist for all the phases considered. Thermodynamic data for multicomponent solution phases are based on the thermodynamic data of the end-member components and on the interaction parameters of the solution model describing the Gibbs energy of the solution phase. Thermodynamic modeling is also important in kinetic modeling [23] and in modeling diffusion in alloys [24]. The computational methods involved in calculating multiphase multicomponent thermodynamic chemical equilibrium revolve around Gibbs energy minimization [23]. The classical method of calculating the phase equilibrium from equilibrium constants is not suitable for large multicomponent multiphase systems. The true chemical equilibrium can be calculated by considering the Gibbs energy of all phases and minimizing the total Gibbs energy of the system (G). Here, G can be

calculated either from the knowledge of the chemical potential (

by

G , μ i ) of component i,

i

G

=

i

n G

i

i

,

[Eq. 3.1]

where n i is the amount of component i, or alternatively by

G

=

φ

φ

N G

φ

m

,

[Eq. 3.2]

where N φ is the amount of the phase and

For a given set of constraints, such as fixed P, T, and overall composition, the Gibbs energy minimization algorithms find the amounts of the various phases and the composition of the solution phases which give a global minimum in the total Gibbs energy of the system. One of the best-known Gibbs energy minimization programs is

G

φ

m

is the Gibbs energy of the phase.

Chapter 3-Thermodynamic modeling

SOLGASMIX by Eriksson [25]. This program has evolved over the years and is currently an integral part of the thermochemical software package FactSage [26]. In the present study, all thermodynamic calculations were performed using FactSage. Several other programs have also been developed for thermochemical calculations. An entire issue of the Calphad Journal is dedicated to reviews of many existing programs (Volume 26, issue 2, 2002).

3.3 Optimization of phase diagrams and thermodynamic data

Phase diagrams and phase equilibria can be calculated if the Gibbs energy functions of all phases involved are known. If the Gibbs energy functions for a phase are not known but experimental data for phase equilibrium or thermodynamic properties exist, it is possible to obtain a thermodynamic description of the phase through an optimization procedure, often called the Calphad method. The principle underlying the Calphad method is to obtain a set of consistent Gibbs energy functions for all phases in the system of interest by using experimental thermochemical and phase equilibrium data as input [27]. In many cases, the main emphasis is on optimizing the Gibbs energy functions of the solution phases, which in reality means optimizing the interaction parameters of various solution models. The Gibbs energy functions are obtained by weighted nonlinear optimization of the thermochemical and phase equilibrium data. Several of the commercially available thermodynamic software packages include programs for these optimization. The Optisage module in FactSage [26] was used in the present study. The optimization algorithm in the program is a nonlinear Bayesian least squares technique [28-30]. The general procedures for optimizing phase diagrams and thermodynamic data with the Calphad method are described by Hari Kumar and Wollants [27] and Schimd-Fetzer et al. [31].

Chapter 3-Thermodynamic modeling

3.4 Thermodynamic models of ionic solutions

The thermodynamic properties of solution phases as function of composition must be known to calculate phase equilibrium involving the solutions. For this purpose, different thermodynamic models have been developed to describe the thermodynamic properties of solutions. Solution phases are the gas phase, liquid phases and solid solutions. The gas phase is a solution phase, which shows complete miscibility of all gas species. The non- ideal behavior of the gas phase can be modeled by several different approaches. The van der Waals equation was one of the first steps to introduce nonideality to the behavior of real gases, taking into account the interaction between gas molecules. At the high temperatures and the atmospheric pressure in a kraft recovery boiler, the non-ideality of gases is usually not very pronounced; therefore, models for the nonideality of gases is not treated further in this work. The solution models that are treated in more detail have been developed for solid solutions or liquid solutions. Several of these models are often used for both solids and liquids. For all solution phases, the Gibbs energy is given by the general formula

G = G° + ΔG

ideal

mix

+ G

excess

mix

,

[Eq. 3.3]

where is the contribution of the pure components of the phase to the Gibbs energy,

is the excess Gibbs energy of mixing,

which is the contribution involving the non-ideal interactions between the components.

ΔG

ideal

mix

is the ideal mixing contribution, and

G

excess

mix

3.4.1 Ideal solutions

The simplest solution model is an ideal substitutional solution or the Raoultian solution. This approach is valid for an ideal gas phase and may be valid for simple metallic liquid or solid solutions, where the components show very similar behavior. The ideal substitutional solution is characterized by random distribution of components on one lattice with an interchange energy equal to zero. For the gas phase and liquids, no actual lattice exists as the crystallographic structure is lost, but for modeling purposes a quasi-

Chapter 3-Thermodynamic modeling

lattice or defined spatial positions are used to model the mixing of particles. For an ideal

) is zero, and as it is

assumed that there is no change in bonding energy or volume upon mixing, the enthalpy of mixing is also zero:

substitutional solution, the excess Gibbs energy of mixing (

G

excess

mix

ΔH

ideal

mix

=0.

[Eq. 3.4]

The Gibbs energy of mixing is therefore given by the following expression:

ΔG

ideal

mix

= −TΔS

ideal

mix

.

[Eq. 3.5]

The term

deals with the entropy associated with random distribution of particles over a given

number of positions, and

is related to the Boltzmann equation for configurational entropy, which

ΔS

ideal

mix

ΔS

ideal

mix

is given by the following expression:

Δ

S

ideal

mix

= −

R

i

x

i

ln x

i

.

[Eq. 3.6]

The molar Gibbs energy of an ideal solution is

G

m

=

x G

i

o

i

+

RT

x

i

ln x

i

i i

, [Eq. 3.7]

where

solutions are uncommon for condensed phases as there usually is some interaction between the components of the solution.

o is the Gibbs energy of the phase containing the pure component i. Ideal

G

i

3.4.2 Nonideal solutions

The regular solution model is the simplest thermodynamic model for nonideal solutions. The regular solution model considers that the magnitude and sign of the interactions between components in a phase are independent of composition. If the total energy of the solution (E 0 ) originates from only nearest-neighbor bond energies in a system A-B then

E 0 =ω AA E AA +ω BB E BB +ω AB E AB ,

[Eq. 3.8]

Chapter 3-Thermodynamic modeling

where ω AA , ω BB , ω AB are the number of bonds and E AA , E BB , E AB are energies associated with the formation of different bond types AA, BB and AB. If there are N atoms in the solution and the coordination number for nearest-neighbors is Z, the number of different bond types formed in a random solution will be

ω

AA

=

ω =

BB

1 NZx

2 A

1

2

2

B

2

NZx

ω

AB

= NZx x

A

B

,

[Eq. 3.9.1]

,

[Eq. 3.9.2]

,

[Eq. 3.9.3]

where x A and x B are the mole fractions of A and B. By substituting Equations 3.9.1-3.9.3 into Equation 3.8, the total energy of the solution will be given by the expression

B

E

0

=

NZ

2

(

x

A

E

AA

+

x

B

E

BB

+

x

A

x

B

(2

E

AB

E

AA

E

BB

))

. [Eq. 3.10]

By subtracting the energy of pure A and pure B from Equation 3.10, the energy change for mixing A and B to an A-B solution will be

ΔE =

NZ

2

(

x

A

x

B

(2

E

AB

E

AA

E

BB

))

.

[Eq. 3.11]

One can approximate that ΔEΔH mix , where ΔH mix is the enthalpy of mixing. If the bond energies are temperature-dependent, there will also be a term for excess entropy of mixing, which can be derived in a similar fashion as for ΔH mix . The excess Gibbs energy of mixing for the regular solution model is given by

G

excess

mix

= Δ

H

mix

Δ

T

S

excess

mix

=

x

A

x

B

Ω

,

[Eq. 3.12]

where Ω is a composition-independent, temperature-dependent interaction parameter. The general expression for the Gibbs energy of a regular solution is as follows:

G

m

=

i

x G

i

o

i

+

RT

i

x

i

ln x

i

+

∑∑

i

j

>

i

x x

i

j

Ω

ij

. [Eq. 3.13]

However, it has been realized that the assumption of composition-independent parameters for the excess Gibbs energy is too simple for many systems. The approach where the interaction terms change linearly with composition is called a subregular

Chapter 3-Thermodynamic modeling

solution model. Even more complex compositional dependencies can be adopted. The Redlich-Kister form, (x A -x B ) , where n is a positive integer, is a common form of expressing composition-dependent terms of the excess Gibbs energy. The Gibbs energy of the solution with the excess Gibbs energy expressed in Redlich-Kister form is

B

n

G

m

=

i

x G

i

o

i

+

where the term

RT

Ω

i

n

ij

x

i

ln x

i

+

∑∑

i

j

>

i

x x

i

j

n

Ω

n

ij

(x

i

x

j

)

n

, [Eq. 3.14]

is a binary interaction parameter dependent on the value of n.

Equation 3.14 will reduce to Equation 3.13 if n=0. According to Saunders and Miodownik [23], the value of n does not usually go above 2. If higher power expansions are needed to describe G excess , an incorrect model has probably been chosen to model the solution. Other equivalent polynomial expansions, such as a simple power series or Legendre expansions are also used [32].

3.4.3 Sublattice models

Simple nonpolar molecular solutions and ionic solutions, such as molten salts, often exhibit approximately regular solution behavior according to Pelton [33]. Sangster and Pelton [34] showed that the liquid phase and solid solutions in many of the binary common-anion or common-cation systems of alkali halides can be modeled with regular or subregular solution models. However, substitutional solution models are not suitable for more complex ionic solutions with several cations and anions, or where there is a strong ordering of the components in the liquid phase, which is the case for some alkali halide-alkaline earth halide systems. In a review of thermodynamic models for molten salts and slags, Pelton [35] showed that an associate model will not predict the phase equilibrium satisfactorily for ionic solutions, such as K + , Li + //Cl - , F - , where LiF, LiCl, KF and KCl are the solution components. Instead, models that take into account physical properties of the ionic

Chapter 3-Thermodynamic modeling

solutions are needed. Temkin [16] was one of the first to propose a thermodynamic

model of ionic solutions, in which two sublattices are considered. The cations reside on

one sublattice and the anions reside on the other sublattice. The configurational entropy is

governed by the site occupation of the various cations and anions on their respective

sublattices. For a simple reciprocal ionic solution A, B/X, Y, where the cations A and B,

and the anions X and Y have the same absolute value of their ionic charge, the Gibbs

energy of the solution is given by the following expression:

G

+

cation

A

anion

X

cation

B

=

m

x

cation

B

x

x

ln(

x

o

AX

G

))

+

+

x

(

RT x

cation

A

x

anion

X

anion

Y

G

o

AY

anion

X

+

)

ln(

x

x

+

x

cation

B

x

anion

Y

anion

X

G

x

o

cation

B

anion

Y

BX

anion

Y

+

x

))

x

.

ln(

+

G

E

o

G

BY

+

(

RT x

cation

A

[Eq. 3.15]

ln(

x

cation

A

)

The term

x

sublattice is the site fraction of a sublattice component i on the sublattice, and

i

is the Gibbs energy of the pure component AX. If the valence of the cations and

anions varies, the modeling will become more complex. Pelton [36] developed a

sublattice model for molten salts, in which equivalent cationic and anionic fractions are

used instead of site fractions. The equivalent fractions are defined as

G

o

AX

Y

i

=

q n

i

i

/

i

q n

i

i

.

[Eq. 3.16]

The term q i is the absolute charge of the ion i, and n i is the number of moles of i on the

sublattice. The Gibbs energy of the solution is given by the expression

G

m

=

∑∑

A

X

Y Y

A

X

G

o

AX

+RT

((

q

X

x

X

)

1

(

x

X

ln

x

X

)

+

(

q

A

x

A

)

1

(

x

A

ln

x

A

))

+ G

E

[Eq. 3.17]

.

A thermodynamic database for the Li + , Na + , K + //F - , Cl - , OH - , CO 3 2- , SO 4 2- system has

been developed using the sublattice model for molten salts [36], which gives good

estimates of the thermodynamic properties of multicomponent liquids.

Hillert et al. [18] also developed a sublattice model for ionic solutions, which is

known as the ionic two-sublattice model for liquids. The model can accommodate

hypothetical charged vacancies and neutral species on the anionic sublattice, meaning

Chapter 3-Thermodynamic modeling

that the solution composition can vary between a metallic state and a fully ionized state.

More in-depth descriptions of the sublattice models are given by Pelton [36] and Hillert

et al. [18].

3.4.4 Compound Energy Formalism

The Compound Energy Formalism is a mathematical formalism, which is commonly

used for describing the thermodynamic properties of solutions that are modeled with

sublattice solution models. In the present work, the thermodynamic properties of all

multicomponent solid solutions are described using the Compound Energy Formalism

[37, 38].

Sodium and potassium salts, such as sulfates, disulfates, carbonates, and

chlorides, tend to form complex solid solutions. In general, these solid salt solutions can

be considered to consist of sublattices, which contain the ionic components. In the

simplest case with two sublattices, one sublattice contains the cations, such as K + and

Na + , and the other sublattice contains the anions, such as SO 4 2- and CO 3 2- . More

complicated sublattice configurations may be considered. The solid solution might have

several cationic crystal sites, where one cation is preferred on one site, and another cation

is preferred on another site. A classical example is the spinel phase, AB 2 O 4 , where A 2+

resides on sites with tetrahedral coordination, and B 3+ resides on sites with octahedral

coordination. The phase can be considered to consist of three sublattices, as O 2- resides

on a third, anionic sublattice.

For the reciprocal solution phase (A,B) m (C,D) n , where the species A and B reside

on the sublattice S, and the species C and D reside on a second sublattice T, the molar

Gibbs energy of the solution is given by the following expression:

G

+

m

(

S

T

y

mRT y

=

A

y

(

C

G

o

:

A C

S

A

ln

y

+

S

A

y

+

S

A

y

T

D

G

o

:

A D

y

S

B

ln

y

S

B

+

S

B

T

C

G

(

o

+

y

)

y

:

B C

T

C

+

nRT y

ln

y

S

B

y

T

C

T

D

o

y

+

G

:

B D

y

T

D

ln

y

T

D

))

+

G

E

.

[Eq. 3.18]

Chapter 3-Thermodynamic modeling

The first four terms give the reference Gibbs energy of the solution, where

y

S

A

is the site

fraction of species A on sublattice S,

member component A m C n , and correspondingly for the other sublattice species and end- member components. The two following terms give the ideal entropy of mixing (Temkin type [16]), assuming a random distribution of the sublattice species on their respective sublattices, and the final term is the molar excess Gibbs energy. The excess Gibbs energy is given by the following expression:

is the standard molar Gibbs energy of the end-

G

o

:

AC

G

E

=

y

S

A

y

S

B

y

T

C

L

A B C

,

:

+

y

S

A

y

S

B

y

T

D

L

A B D

,

:

+

y

S

A

y

T

C

y

T

D

L

AC D

:

,

+

y

S

B

y

T

C

y

T

D

L

B C D

:

,

+

y

S

A

y

S

B

y

T

C

y

T

D

L

A B C D

:

,

,

[Eq. 3.19]

The four first terms are interaction parameters of the four binary subsystems, and the last term is a reciprocal interaction parameter. The L factors can be temperature- and composition-dependent, commonly given as Redlich-Kister terms as function of the site fraction.

3.4.5 Modified Quasichemical Model in the Quadruplet Approximation

The regular solution model and modifications of it, together with sublattice models mentioned above, assume that the mixing of particles is random, even when the excess Gibbs energy is not zero. However, several systems show considerable short-range ordering in the liquid phase, especially oxide systems where polymeric units are present. Examples are silicate, borate and phosphate liquids. Similar strong short-range ordering can be found in many binary liquids consisting of alkali halides together with divalent or trivalent metal halides. The Quasichemical Model was developed by Guggenheim [39] and Fowler and Guggenheim [40] to take into account non-random short-range ordering in solutions. Pelton and Blander [41] and Blander and Pelton [42] modified the model, with further developments made by Pelton and Chartrand [43], Chartrand and Pelton [44], and Pelton et al. [17, 45], by making the model more flexible and by merging the

Chapter 3-Thermodynamic modeling

quasichemical model with sublattice models. The article by Pelton et al. [17] on the Modified Quasichemical Model in the Two-Sublattice Quadruplet Approximation is the latest development of the Modified Quasichemical Model, permitting the treatment of both first-nearest-neighbor and second-nearest-neighbor short-range ordering simultaneously in molten salt solutions. For the liquid solution, the thermodynamic model must take into account cations and anions being distributed on a cationic and an anionic quasi-sublattice. If there are two or more cations and two or more anions in the solution, the phase will be a multicomponent reciprocal solution. Large deviations from ideal mixing can occur in reciprocal molten salt solutions due to the strong first-nearest-neighbor (cation-anion) interactions. Simultaneously, strong second-nearest-neighbor (cation-cation, or anion- anion) interactions can occur, making modeling of such systems difficult. The Modified Quasichemical Model in the Two-Sublattice Quadruplet Approximation [17] was used in the present work to model the Gibbs energy of the liquid phase. This model was developed particularly for molten salt solutions that exhibit strong short-range ordering (SRO) between ions of opposite charges (first-nearest- neighbours, FNN) and between ions of the same charge (second-nearest-neighbors, SNN). The Modified Quasichemical Model in the Two-Sublattice Quadruplet Approximation simultaneously evaluates the impact of all FNN exchange pair reactions (similar to Eq. 3.20) and all reactions involving SNN pairs (similar to Eq. 3.21.1 and 3.21.2) on the configurational entropy:

[

[

[

K

CO

3

][

pair

+

Na

Cl

][ pair

=

K

K

Na

Na SO Na

4

CO

3

Na

CO

3

][

pair

][

pair

+

+ K SO

4

SO

4

Cl

]

]

pair

pair

=

+

[

Na

CO

3

] pair

2

[

Na SO K

4

]

Δ

g

K Na

,

/

CO

3

,

Cl

pair

Δg

Na, K / SO

4

.

,

[Eq. 3.20]

[Eq. 3.21.1]

SO

4

]

pair

= 2

[

CO

3

Na

SO

4

]

pair

Δg

Na / CO ,SO

3

4

.

[Eq. 3.21.2] If the standard Gibbs energies of Eq. 3.20 and Eq. 3.21 are negative, the equilibrium will be shifted to the right and FNN and SNN pair concentrations will be affected accordingly (resulting in FNN SRO and SNN SRO). If the values of the standard Gibbs energies of Eq. 3.20 and Eq. 3.21 are close to zero, the model will be reduced to a random mixing

Chapter 3-Thermodynamic modeling

model. In the model, each quadruplet consists of 2 cations and 2 anions forming a

configurational unit that includes 4 FNN pairs and 4 SNN pairs. Each quadruplet has

Gibbs energy, and the parameters of the model are the energies of the quadruplet-

formation reactions. The quadruplets mix randomly and are constrained by an elemental

mass balance. Overlapping of sites and pairs is considered in the configurational entropy.

The Gibbs energy of the quadruplets is defined as follows: The Gibbs energy of a

unary quadruplet consisting of two cations A and two anions X is

o

g A

2

/ X

2

=

⎝ ⎜

⎟ ⎠

⎜ ⎝

2

q

A

2 q

X

Z

Z

A

A

2

/

X

2

A

1/

q

A

X

1/