Kraft Recovery-

The effect of sodium sulfide on the equilibrium of the causticization reaction

John C. Ransdell andJoseph M. Genco
Graduate assistant and professor of chemical engineering, Dept. of Chemical Engineering, University of Maine, Orono, Me. 04469

ABSTRACT The causticizing reaction equilibrium was studied experimentaly. In the &raftcausticization reaction, sodium bydroxide is regenerated b y solid calcium hydroxide reacting with aqueous sodium carbonate solution in the presence of sulfide and other ions. Fifty-eight causticization qeriments were performed at sulfidity levels o f 0%,15%, and 30%.The data could be explained in terms of a thermodynamic mode4 the basis for which is an estimation for the activity coefficientsfor C0:- and OH- ions in strong electrolytes. The current work. extends the theoretical model to include the effect of the sulfide ion. A set of ion interaction parameters and the thermodynamic equilibrium coefficient were obtained from the equilibrium data. Causticization efficiencies can be obtained based on the use of the model with the experimentally determined parametm
In the kraft pulping process, the chemical recovery step of causticization is utilized to regenerate sodium hydroxide. The causticization reaction is an exchange of hydroxide ion from slaked lime with carbonate ion in solution. able to obtain as low a level of carbonate ion as possible in the white liquor solution. The causticizing efficiency, E, is given by the relationship discussed by Hough (3):
E = 100%x [NaOH y [NazCOs ]
(2)

KEYWOORDS Causticizing Chemical recovery Kraft liquors Kraft pulping Sodium hydroxide Sodium sulfide Thermodynamics

constant calculated in concentration units, K,,was the same for both carbonate solutions, with and without sodium sulfide. This equilibrium constant is calculated as:

K,= [OH-]'/ [CO;']

(3)

In the causticization reaction, an equilibrium exists that depends primarily on the cationic sodium concentration of the solution and secondarily on the temperature. Pressure has little effect on the thermodynamic equilibrium because liquid-phase reaction occurs (1, 2). The extent of the conversion of sodium carbonate to sodium hydroxide in the process is important in regard to the efficient operation of the kraft recovery operation. It is desir-

where [NaOH] is defined as the sodium hydroxide concentration in the white liquor less the concentration of sodium hydroxide in the green liquor and [Na~C03 ] is the concentration of sodium carbonate in the green liquor.

Related research
Considerable early work has been published on causticization of sodium carbonate (4-11). Rydin and coworkers ( 1 2 )studied the effect of lime quality on the equilibrium. Kojo (1315) concluded that the equilibrium

The units for [OH- ] and [c03'- ] are moles per liter of solution. Lindberg and Ulmgren ( 1 , Z ) determined the effects of the major variables of concentration, composition, and temperature on the causticization equilibrium. The theoretical equilibrium constant for the reaction was expressed in terms of activity coefficients. The activity coefficients were assumed to be independent of the solution composition, provided the concentrations of inert cations Na' ' , with opposite signs to the and K O : , . remained reactants OH- and C constant in a medium of high total
August 1991 Tappi Journal

169

concentration. They concluded that the cation concentration was the parameter of greatest influence on the magnitude of the equilibrium constant and that temperature had little effect. Lindberg and Ulmgren were able to fit their data accurately to the following empirical equation:
log K, = 2.95 - 0.62 x ( [Na' 1 + [K'

to quantify an estimate for the activity coefficient constant K,(T, X), in which ' A represents the ionic composition of the system. Daily and Genco established the basic relationship of Eq. 7 for describing the equilibrium condition for the causticization reaction.
See Equations 7-11.

1)''

(4)

The presence of hydrosulfide ( H S ) had no effect on the equilibrium constant but was shown to have a slight effect on the degree of causticizing as a result of the increase in the total cation concentration.

Thermodynamic considerations
,

Genco and Daily proposed a semiempirical model for the causticization reaction, based on the fundamental thermodynamic equations governing chemical equilibrium in electrolytic solutions (16, 17). For this reaction, the thermodynamic equilibrium constant, K(T), is given by the relationship:
In K( r ) = In [K. (T,X ) x mZoH-/ mco3= 1 = AG"/R T (5)

where
K.(T, X )
mOH

= activity coefficient constant = [OH- ] expressed in molality units of g moles/ 1000 g water

mcos=

+ [CO;. 1 expressed in molality units of g moles/ 1000 g water

= temperature = universal gas constant.

In Eq. 5, A G O is the Gibbs free energy charge for the reaction if it occurs in the standard state. The units used to describe the equilibrium are arbitrary. The units of molality are often used because the concentration terms are independent of the solution density. Using molality units, the equilibrium constant, Eq. 3 becomes:
K, = mZoH-/ mcog=
(6)

In this model, m and x are the molalities and valences of the major ionic species in solution-that is, the sodium, hydroxide, carbonate, and bisulfide ions. A0 is the Debye-Huckel parameter given by Pytkowicz (22) for water at 100C (A' = 0.4603), and a is a constant for the Pitzer equations (0 = 2.0). The functionsf: gl(l), and g2(4 are calculated from the value of the ionic strength, I , by Eq. 11. The model has six parameters; the thermodynamic equilibrium constant, K(T), and the Pitzer ion interaction parameters pt:l, Ct:l, pB3!oH-, p*,',ll,co=, P*N(aliHS-, which describe the interaction of' ion pairs. For example, the parameter p::) is used to describe thermodynamic interaction of cationic sodium ion with anionic carbonate ion and anionic hydroxyl ion. The Pitzer parameters are similar to second and third virial coefficients used for describing the thermodynamic properties of gases and vapors. The practical value of Pitzer's work is that it permits an analytical expression to be written for the activity coefficient constant K,( T,X) and thus gives the proper theoretical form for the causticization equilibrium equation (Eq. 7). Thus, one does not have tci resort to fitting an arbitrary empirical equation. Theoretically, the six unknown parameters in the model can be determined from an analysis of the product reaction and a linear regression analysis, since the model equation is linear in the six unknown parameters. Daily and Genco studied the causticization reaction for pure sodium carbonate (17).They solved for five of the unknown parameters in the model by the method of linear least squares. In this analysis, the quantity Y was estimated from the experimental data and the calculated function 2fy.

ion, they omitted the reaction parameter p HS-, which describes the interaction of sodium ion with bisulfide ion. Not all of the parameters were found to be statistically significant when the equilibrium data were fit to the model. Rather, for the causticization of pure NaZC03 with Ca(OH)2, a principal component analysis reduced the number of parameters to two. These two parameters were In K(T) and P*(')N, +. The reduced form of the model is given by Eq. 13 (17).
See Equation 13.

where the thermodynamic equilibrium constant In K(T) and the Pitzer parameter p*('ha + had the values 7.27 and -0.193, respectively.

Objective
Our objective in this work was to experimentally determine the effect of sulfide ion on the causticization equilibrium. We wished to extend the model proposed earlier (16, 17) to include the effect of sulfide ion. Another goal was to determine the Pitzer parameter &$! HS-, describing interactions of sodium with bisulfide ions.
,

Results
The apparatus, experimental procedures, and method of estimating the equilibrium coefficients K, and K, are summarized in the experimental procedures section. Details of the experimental procedures and a summary of the data are presented elsewhere (23,24). Causticization efficiencies were calculated from Eq. 2. The values for In K, (Eq. 3) were obtained from an analysis of the data for causticization solutions at equilibrium. The values of the term In K, for 15%and 30% sulfidity (23) were combined with values obtained at 0% sulfidity by Daily (24). All the data were compared to values obtained from the empirical model (Eq. 4) suggested by Lindberg and Ulmgren ( I , @ . All of the experimental data are shown in Fig. 1, together with the line proposed by Lindberg and Ulmgren. Figure 2 is a graph of the equilibrium constant In K, plotted against sodium molality, for the total set of 58 caus-

See Equation 12. Based on this fundamental relationBecause their experiments were ship, Daily and Genco ( 1 6 1 7 )used the work of Pitzer and eo-workers (18-21) performed in the absence of sulfide

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August 1991 Tappi Journal

1. In K , vs. total sodium ion concentration, showing model line of

2. In K , vs. total sodium for O%, 15%, and 30% sulfidity

Lindberg
5.5
5.0
L

I
E Y
C

fie

4.5

4.5

.
Sulfidlty
0

2
C

- 4.0
3.5

- 0%
0

- 4.0
3.5
'

0%

0%

0 15%

0 15%
0

30%
I

3.0 0.5

30%
I

3.0

1.5

3.5 4.5 TOTAL SODIUM, g moleslL

2.5

5.5

0.5

I
5.5

1.5

2.5

3.5

4.5

TOTAL SODIUM, g m o l e d l

ticization experiments having sulfidand 30%. ities of 0%,E%,

causticizations and are given in Table

I.
Unfortunately, the significance levels of the six unknown parameters were determined to be low. This determination was made by estimating the confidence limits or standard error on the model coefficients using the SAS computer program. The confidence levels on the six coefficients are thought to be low because the independent parameters in the model are not truly independent of

Discussion: treatment

o f experimental data
Least square d y s i s

A least squares analysis was performed on the data using the SAS'" statistical analysis system computer program (25). Values for the model parameters were numerically calculated over the entire data set of 58

each other but vary in a colinear manner. Thus, it is difficult to estimate all six coefficients directly from the causticization reaction equilibrium and come out with narrow confidence limits. Rather, each of the coefficients would have to be determined in independent experiments and then combined in Eq. 7 to predict the causticizing equilibrium.
Principal component analysis

Here, the model may be simplified

August 1991 Tappi Journal

17%

1. Least squares estimation of the equilibrium model coefficients and the eigenvalues obtained by principal component analysis
Least squares analysis Standard Value error Principal component analysis Principal commnent Eigenvalue Cumulative contribution

Parameter

In K(T)

7.94 0.910 3.52 -0.0701 -4.71 1 2 . 1

f1.26 k0.664 f5.57 f0.0535 f5.76 f15.7

4.50734 0.8 8955 0.56241 0.03943 0.00125

0.75122 0.89948 0.99322 0.99979

pig! fl;:, HSC Na+

2 3 4

flirJg OHp Na+, (1) Cog

5
6

1 .ooooo
1 .ooooo

0.00001

( 1 7, 23). The diagnostic technique

termed the principal component analysis was used to examine the influence of each parameter on the solution of the model. The eigenvalues for the principal components of the model are summarized in Table I. For three of the principal components, the eigenvalues are significant. The eigenvalues of the fourth principal compoof the eigenvalue of nent is below 1% the first principle component. For statistical significance, differences in magnitude between the eigenvalues of each of the parameters would need to be low. A low difference between the eigenvalue for the first component and each subsequent component would indicate that the addition of the subsequent component was significant in the solution of the model. For the data set, the significance of the fourth and subsequent principals is low. Therefore, based on the principal componentanalysis for the data set, the number of model unknowns and coefficients should be reduced to three in order to eliminate the potential for over-specifying the model. Statistically, any three of the model coefficients can be chosen to fit the data, and a good fit would be obtained. However, based on physical-chemical considerations, we chose the equilibrium coefficient In K(T) and the Pitzer parameters &$I and & . $ : SH-. Following our early results ( 1 7) for causticizing pure sodium carbonate, the reduced model equation was chosen to be:
See Equation 14,

where gz (I), and I are given in Eqs. 8, 10, and 11 and AO= 0.4603 and a = 2.0. The solution of the reduced model is given in Table I1 for the complete data set of 58 causticizations, including the standard errors for each parameter. These standard errors are low in relation to the value of the parameters. Note that the significance levels of these values are high. LJsing the best-fit parameters from Table 11,values for the variable In K m can be obtained directly from the model equation as a function of the sodium molality and the sulfidity. Values of In K m determined by the use of the model are plotted as curves in Fig. 3, together with the experimental data points.
Estimation of causticizing efflciency

II. Estimation of the revised equilibrium model coefficients and associated errors
Standard error

Parameter

Value

f0.0209 -0.163 3~0.00589

[NaZS ]

= concentration of sodium

sulfide, g as NazO/kg.

= active alkali, g as NazO/kg The term causticization efficiency AA has been used frequently to describe = NaOH+NazS the quality and degree of the causticization reaction. The model, as developed, can be utilized to determine In Eq. 16, it is assumed that the equilibrium values for the causticiza- hydrolysis of the sulfide ion is comtion efficiency, given the total cation plete, according to the following concentration of the solution and its reaction (26): sulfidity:

S=+ H z O ,

SH-+OH-

(18)

= (TTA/31)
mHs- =
x

23

(15) (16) (17)

sulfidity)/2

sulfidity = [Na2S]/AA

The electrical neutrality condition for the system can be used as a constraint:

where
TTA
= total titratable alkali, g as Na~O/kg = NaOH + NazS + NaC03 + /z NaZS03

The causticizing efficiency can be estimated by solving simultaneously Eq. 6 for the equilibrium coefficient K, and Eq. 19 for the concentration

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August 1991 Tappi Journal

3. In K , vs. total sodium for 0%, 15%, and 30% sulfidity and the reduced equilibrium model

1
5.5,
1

E
4.0

- E

3.5

:::
4.0

0% SuHldky

-._

- model

38

-.TOTAL SODIUM, g moldkg

3.0

- model

30% Sulfldlty

\
TOTAL SODIUM, g mole/kg
175

TOTAL SODIUM, g moldkg

4. Causticization efficiency vs. total titratable alkali for 0%, 15%, and 30% sulfidity data and the reduced equilibrium model

85-

.
TOTAL TITRATABLE ALKALI, as NazO/L

- model
55

15% Sulfidity

85

115

145

5 17!

25

55

85

115

145

TOTAL TITRATABLE ALKALI, as Na,O/L

TOTAL TITRATABLE ALKALI, as NazO/L

of carbonate ion, mco; to get Eq. 20:

See Equation 20.

represent the experimental d a t a extremely well.

In the solution, values for the sodi- Conclusions um and bisulfide molalities must be given to determine a value of K, using Sulfidity has an effect on the equilithe model equation, Eq. 14. The brium coefficients K, and K,. With hydroxide molality can then be deter- sulfide ion added to green liquor, the mined using Eq. 20. Once the value reaction is somewhat suppressed, and of the hydroxide molality is known, the equilibrium coefficient (K, or K,) the carbonate molality may be calcu- is lower. This less active reaction results in less carbonate ion being lated from Eq. 19. converted to the solid form and less For this system a t equilibrium: hydroxyl ion being formed. E = OH- - WLHC)/ The unknown parameters in the (mH' -m H S - + 2"CO;) (21) thermodynamic model were evaluatTTA = [NaOH] + [NazCOs] + [NazS] (22) ed from the composition data determined for the reaction at equilibrium. Figure 4 present plots for the However, the statistical significance equilibrium causticizing efficiencies of the six unknown parameters was determined experimentally and by low. The model equation is thought to use of the model equation. As these be over-specified in relation to the graphs show, the model equations quality and size of the data set and the

fact that the independent variables in the model vary colinearly. With interpretation of a principal components analysis of the data and the model, the equilibrium model equation was reduced to three unknown parameters and coefficients. This reduced model, Eq. 14, fits the data set well, and the significance of the unknown model parameters is high. The model equation can be used to predict the equilibrium causticization efficiency, given only the sodium molality and sulfidity.

Experimental method * P P "

Sodium carbonate solutions having various levels of sodium sulfide were reacted with calcium hydroxide in a constant-temperature, stirred-tank, batch reactor at 100C (Fig. 5). The
August 1991 Tappi Journal

173

If

111. Example of results of causticization product analysis at 30% sulfidity

I
Molal concentration, moleslL Na+
OH-

Molar concentration, g moleslL

Run Na+

OH'

COS'

HS-

lnK,

Conc. of Densit% water, kg H20IL kglL

Cog'

HS-

lnKm

39 35 3 1 27 25 48 34 38

1 . 7 2 8 1 2.1949 2.6646 3.0988 3.4510 3.9711 4.5214 4.9962

1.4492 1.8125 2.1733 2.4600 2.7200 3.0484 3.3516 3.6000

0 . 0 1 6 12 1 0.033714 0.061454 0.090242 0.120492 0.183068 0.260682 0.337273

0.2467 0.3150 0.3683 0.4583 0.4900 0.5567 0.6483 0.7217

4.87 4.58 4.34 4 . 2 1 4.12 3.93 3.76 3.65

1.068 1.087 1.104 1 . 1 1 8 1 . 1 3 1 1.153 1.173 1.189

0.9945 0.9933 0.9899 0.9844 0.9820 0.9805 0.9750 0.9688

1.7377 2.2098 2.6917 3.1480 3.5144 4.0504 4.6373 5.1571

1.4572 1.8248 2.1954 2.4991 2.7699 3.1091 3.4376 3.7159

0.016210 0.033942 0.062080 0.091677 0.122704 0.186716 0.267373 0.315943

0.2481 0 . 3 1 7 1 0.3721 0.4656 0.4990 0.5678 0.6649 0.7449

4.88 4.59 4.35 4.22 4 . 1 4 3.95 3.79 3.68

reaction vessel was constructed from 5. Design of the basic causticizing apparatus stainless steel and had a volume of 1.2 L. The reactor was sealed to 15 psig with Teflon block covers. Reaction access and mixing were provided by a sealed aperture and a sealed bearing assembly in the cover. An in-line Teflon filter (10 pm) and a stainless steel heat exchanger were utilized in removing the product and cooling. The temperature within the reactor was measured using a stainless steel thermocouple and a data logger. The temperature was controlled by immersing the reaction vessel in a constant temperature bath of 100C composed of 60% glycerin and 40% water.
C h e m i d pteparation

and product analysis

Causticizing reactions were conducted with sodium carbonate and sodium sulfide solutions with concentrations ranging from 1.5 to 5.25 g moles Na'/ L, increased stepwise in increments of 0.25 g moles/L. The reactants were of reagent chemical grade. Calcium hydroxide was added in the reaction sequence in an excess of 125% of the amount required to stoichiometrically convert all of the carbonate to hydroxide. The reaction products-sodium hydroxide, sodium carbonate, and sodium sulfide-were analyzed using the titration analysis techniques described in TAPPI Test Method T 624, Scandinavian SCAN-N 2:63 (27), and elsewhere (28). The carbonate ion concentration determined from titration results is considered a less accurate representation of the true value than values obtained by the gravimetric or conductivity techniques. Therefore, the carbonate ion concentration

Settling zon;

11

Constant-temperature bath (100C)

was also determined using gravimetric techniques described in TAPPI T 624.

Experimental procedure

For causticizations, distilled, deionized water and sodium sulfide solution were added to the reactor. To prevent oxidation of the sodium sulfide solution, the solution was stored under a nitrogen atmosphere. Granular sodium carbonate was added to the reactor, and the reagents were

mixed a t 100C for 15 min. Calcium hydroxide was added, and the reactor was sealed for a minimum causticization period of 2 h. For an additional 2-h period without mixing, the calcium carbonate and hydroxide solids were allowed to settle prior to sampling.
Estimation o f the equilibriwn coefficients

The ion concentrations were converted to molalities, given the solution

174

August 1991 Tappi Journal

density by the following equations:

mi =

c;/( P . 4 s )

(23) (24)

izing reaction, J. Pulp Paper Sci., paper submitted for publication, 1991. 18. Pitzer, K. S., J. Physical Chemistry
77(2): 268(1973). 19. Pitzer, K. S. and Mayorga, G., J. Physical Chemistry 77(19): 2300( 1973). 20. Pitzer. K. S. and Kim.. J.. . J. Am. Chem. SOC. 96( 18): 5701( 1974). 21. Pitzer, K. S., Activity Coefficients in

[HzO ] = ( p s - CJ

C. = [NaOH I MW,,oH + [CaCO, 1 MWc.cos + [NaHS 3 MWN~HS

(25)

where
mi

= molality of species i, moles/kg

22. 23.

solvent

Ci
ps

= concentration of i, moles/L of

solution
= density of the solution, kg/L

24.

M W = molecular weight.

Table I11 illustrates the experimental data for the case of 30% sulfidity. The equilibrium constants K, and K, were estimated from the concentrations or molalities for hydroxyl and carbonate ions. Solution densities were measured using a Metler/Paar DMS 35 density meter.lJ

25. 26. 27.

Electrolyte Solutions, Vol. I (R. M. Pytkowicz, Ed.), CRC Press, Boca Raton, 1979, Ch. 27, p. 157. Pytkowicz, R. M., Activity Coefficients in Electrolyte Solutions, Vol. I, CRC Press, Boca Raton, Fla., 1979. Ransdell, J., Effect of sulfide ion on the kraft causticizing reaction, M.S. thesis, University of Maine (Dec. 1989). Daily, C. M., A thermodynamic model of the kraft causticizing reaction equilibrium, M.S. thesis, University of Maine (Dec. 1987). SAS User's Guide: Statistics, SAS Institute, Inc., Cary, N.C., 1985. Teder, A. and Tormund, D., Svensk Papperstid. (16): 607( 1973). SCAN-N 2:63, Svensk Papperstid.

H)RSTAINLESS STEEL PIPING, FITTINGSAND ACCESSORB FOR THE PULP AND PAPER
Third Edition. A project of the Maintenance & Mechanical Engineering Committee of the TAPPI Engineering Division. Establishes recommended specifications for corrosion resistant pipe, tube, fittings and accessories for the pulp and paper industry. Covers the manufacture and fabrication of corrosion resistant pipe, tube, fittings and accessories which conform to uniform recommendations which mill personnel can use as a guide for purchase and installation. Includes a laboratory corrosion resistance data chart and an International Standard (SI) factors for conversion of customary units.
1986.28 pp., 8'12 x B 1 soft-cover Order Number: 01 01 R133 TAPPI Members: $30.12; list: $44.95

66( 18): 727( 1963). 28. Causticizing, Pulp and Paper Manufacture-the Pulping of Wood, Vol. 1,

2nd edn. (R. G. MacDonald, Ed.), McGraw-Hill, New York, 1969, p. 532.
The authors wish to express their sincere appreciation to the U.S. National Science Foundation for the financial support of this work. Received for review July 2, 1990. Accepted Dec. 7,1990. Presented a t the T A P P I 1990 Pulping Conference.

Literature cited
1 . Lindberg, H., and Ulmgren, P., J. Pulp Paper Sci. 9(1): TR-7(1983). 2. Lindberg, H. and Ulmgren, P., 1985

International Recovery Conference Proceedings, TAPPI PRESS, Atlanta, p. 329. 3. Hough, G., Chemical Recovery in the Alkaline Pulping Process, TAPPI PRESS, Atlanta, 1985, p. 201. 4. Lunge, G. and Schmid, J., Berichte der Deutschen Chemischen Gesellschaft,
18: 3286( 1885). Chem. Ind. 45: 5. Goodwin. L. F.. J. SOC. 360T( 1926). 6. Goodwin, L.F. and Sills, J. L., J. SOC. Chem. Ind. 45: 362TU926).
'

7. Olsen, J. C. and Direnga; 0. G., Ind. Eng. Chem. 33(2): 204(1941). 8. Hugher, G. B., Herndon, L. K., and Withrow, J. R., Paper Trade J. TS(Feb. 26): 105(1942). 9. Kobe, K. A. and Wilkinson, J. A., Ind. Eng. Chem. 45(2): 307(1953). 10. Littman, F. E. and Gaspari, H. J., Ind. Eng. Chem. 48(3): 408(1956). 11. Rothbrock, C. W., Tappi 41:
241A(1958). 12. Rydin, S., Haglund, M., and Mattsson, E., Svensk Patterstid. 80(2): 54(1977). 13. Kojo, M., Paperi Puu 61: 244(1979). 14. Kojo, M., Paperi Puu 61: 701(1979). 15. Kojo, M., Paperi Puu 61(8): 515(1979). 16. Daily, C. M. and Genco, J. M., Ther-

modynamics of the kraft causticizing reaction, paper presented at the 1986 AIChE Meeting, Session No. 81, Advances in Chemical Recovery Technology, Part 11, AIChE, New York, 1986. 17. Daily, C. M. and Genco, J. M., Thermodynamic model of the kraft caustic-

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