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Abstract - Reactions of borax with orgatuc acids were studied m a batch mode. Product boric acid resultmg
fixanthe reactionof solid borax with liquid propiouic acid was found to deposit on the surface of the unreaeted
borax core to form an ash layer. Sharp mtefface unreacted core model was used for simulationof this process.
The analytical solution to the model revolvingdiffusion through a liquid boundary film, diffusion through the
solidreactionproducts, and surface reaction was obtained. Reaction of borax solution with oxalic acid crystals
exhibited a different route, i.e., reactive precipitation process. Crystallization of boric acid took place in the
solution phase after complete dissolutionof oxalic acid crystals. Nucleation and growth rates were evaluated
from a series of experiments by the method of s plane analysis. Relative nucleation kinetics were correlated
in terms of the significantprocess variables.
INTRODUCTION
Heterog~eous solid-liquid reactions leading to crystallization of the product are of major importance m the manufacture
of many industrial chemicals. Chemical reactions are usually fast and the resulting product may deposit on the solid
reactant itself without following the conventional precipitation process. Digestion of phosphate ores in sulphuric acid
(Becker, 1983; van der Sluis et. al., 1987; Elnashaie et al., 1990) and conversion of silver chloride crystals by bromine
ions (Zuckerman, 1976; Sugimoto, 1987) are some examples of reaction crystallization in inorgamc heterogeneous
systems in which the conversion takes place on individual reactant particles without nucleation and crystal growth.
Although these type of processes are widely encountered in pracace, information on their modelling and analysis is scarce
in the crystallization literature. Several physical models have been reported for non-catalytic reactions between particles
and fluids. The sharp interface model is frequently considered when fluid reactant diffuses through the fluid film and, if
one is formed, through the porous ash of the reaction product to reach the surface of the unreacted core, where it reacts.
The thickness of ltm product ash layer increases at the expense of shrinkage of the unreacted core keeping the same
overall particle diameter (see, for example, Levenspiel, 1972; Bowen et. al., 1989). On the other hand, if the fluid phase
becomes s u ~ with respect to the reaction product, precipitation from the fluid phase occurs sequentially and/or
coneun'enfly. Reaction crystallization of this type is widely used m the process industries (Doraiswamy and Shamm, 1984)
and conventional process description in terms of conservation of population and mass balances can be employed for their
analysis (Tavar¢ and Garside, 1990). In this paper, these two extreme cases are illustrated by investigating crystallization
of boric acid through reaction of borax with organic acids, although several other alternative possibilities may arise for
solid-fluid reaction systems. Reaction of solid borax crystals and liquid propionic acid to produce boric acid crystals
follows mm-cata~c shg,p interface unreacted shrinking core model (Fig 1.a), while reaction between borax solution and
oxalic acid crystals can be represented by complete dissolution followed by precipitation model (Fig 1.b). The influence
of the different type of organic acids and the addition mode of the reactants on the final product characteristics were
studied and mathematical descriptions developed to interpret the experimental results.
oxak
/
~ a,~a~ B,ri¢ ~ a~at~
"------'4
SolidI~'oduet.." ".
•kl Rmetam
*. . i
r r, Rrc 0 rcR r~ r
Fig 1.a: Sharp interface model Fig l.b: Reactive precipitation model
2547
2548 B.Z. NEZHADet al.
THE SHARP INTERFACE SHRINKING CORE MODEL
The overall chemical reaction between sohd borax crystals and liquid propiomc acid may be written as:
o:_t ~ r c:
cAV v : N,, (2)
R NA~ NA~
dr. 1 (4)
Diffusion through solid product: I): k, f Cl- c,)
Out; c
The relationship between the solid phase conversion, X and the ratio of core radius to particle radius, ~o, is given by:
X W0 - W 1 - ~3 (6)
C
Wo
where W is the overall weight of unreacted solid borax in all particles and W0 the imtial weight of all borax particles. The
molar rate of propioni¢ acid consumption can be related to that of solid phase as:
dv _ dX (7)
dO dO
Noting that propionic acid concentration is in much excess, the variation of propionic acid concentration with solid
phase conversion can be approximated as:
c : co - X = co (8)
Combining eqs (2-8) and integrating the resulting relation using the boundary condition; X = 0 at 0 = 0, the analytical
expression for the variation of dimensionless time with solid phase conversion can he derived as:
Explorato~ studies indicated that boric acid precipitated in the bulk solution when the fluid phase became supersaturated
with respect to product component after complete dissolution of oxalic acid crystals. Precipitation kinetic study is carried
out to correlate the relative nucleation kinetics in terms of process variables. The method of s plane analysis may be
employed to determine the nucleation and growth rates in the Laplace transform domain. The transformed population
density with respect to crystal size is given by:
eo
Laplace transformation of the population balance equation with respect to size under conditions of size-mdependem
growth and zero initial conditions for the newly generated crystals (Tavare and Garside, 1986), and on further
simplification, we get:
Thus eq. 12 can be used to determine the kinetic rates from a pair of population density curves at two sample times At
apart. Nucleation and growth rates obtained by the method of s plane analysis using successive pairs of population density
curves during several runs can be correlated by the relative nucleation kinetic expression as:
B = K R G i M~ N m exp(_Er/RsT) (13)
EXPERIMENTAL
Two types of experiments were used to cany out the overall reactions as in eqs 1 and 10. The first series of experiments
w ~ pefmm3ed in a 1.5 L draft tube baffled (DTB) agitated glass vessel maintained at constant temperature. The content
was stirred by a 4 cm diameter square pitch propeller at a speed to ensure that all particles were completely suspended.
In a typical run a known anaount (1300 g) of propiunic acid was charged into the crystallizer. When the desired
temperature was reached a known amount (130.7 g) of borax crystals of narrow size range was added to start the run.
With this weight ratio of the reactants at the time of borax addition, propionic acid was substantially in excess (25.6 times
the stoichinmetric ratio of borax). Several slurry samples of 20 cm3 were pipetted out at different times and filtered
through a 0.1gtm pore size filter paper. The samples were weighed and finally analyzed for overall compositions of the
solid and solution phases. A weighed aliquot of the dried solid phase was dissolved in water and titrated against standard
acid solution for borax and against standard alkaline solution for boric acid. Samples of solution were analysed for pH
and water content using a pH meter (model PHM84) and an automated Karl-Fischer analyzer, respectively. Propionic
acid and boric acid were determined by titration with standard sodium hydroxide solution and sodium propionate by
sodium ion analysis. In a typical run for the second reaction of borax solution with oxalic acid crystals, the required
amount of filtered borax solution was charged into the crystallizer. In this type of experiment typically 46 g/kg solvent
boric acid was initially dissolved in the feed solutiott Known amount of oxalic acid crystals was added to the solution
at the start of a run. The solid and solution phases were separated by quick filtration of slurry samples withdrawn from
the crystallizer at different times. The solution phase samples were first titrated against standard acid solution for borax.
A 0.1 N manitol solution was used to convert the boric acid into a strong acid. The solution was then backtitrated against
standard alkaline solution for boric acid. The sofid phase samples were analysed for crystal size distribution using a
multichannei Coulter counter equipped with a 400 pm orifice tube. A solution of lsoton II saturated with boric acid was
used as an electrolyte. A series of experiments was performed over the range of variables. The initial molar ratio of oxalic
acid to borax was varied from 0,73 to 1.37, stirrer speed from 8 to 20 Hz, temperature from 20 to 50 °C and size of oxalic
acid crysta~ from 320 to 940 lain
2550 B.Z. NF_,ZHADet al.
Temperature, T, °C 25 20-50
Table 1. Ranges of run conditions and results: borax-propionic acid and borax-oxalic acid systems
• Water
• Boricacid(~ond) ~ 0.
÷ Borax
• Propionle acid 0.6~1 "
~: 0.4- /\ i ,
Boric acid
• Boric acid (liquid) ,- Sodium oxalate i
÷
Model (eq. 9)
0.4t~1/ : v Magma !
0.2 '
Fig 2.a: Concentration profiles in solution and solid phases Fig 2.b: Concentration profiles in solution phase
Borax-oxalic acid system
Borax-propionic acid system 40 i
" 60sec ; ' 180sec • 270sec - - 3 6 0 s
i . . . . . . . . .
16] 30 u
| -w 3600 nC
ae 12 ...-,
>- 2-
:¢ t
,--~
0 100 7.00 300 400 500 700 0 10 20 30 40 50 60 70 80
L,p,m L,Itm
Fig 3.a: Product crystal size distribution Fig 3.b: Product crystal size distribution
Borax-propionic acid system Borax-oxalic acid system
1
10 14 la Lt ~S + +~t~
B = l . 3 x l 0 G N M Exp (-3127/T) + + ~+~ + I
0.8- +~F++ +
Fig 4.a: Comparison of the model with experimental data Fig 4.b: Relative nucleation rate correlation
Fig 5.a: SEM of crystals for the borax-propionic acid system Fig 5.b: SEM of crystals for the borax-oxalic acid system
2552 B.Z. NEZHADet al.
CONCLUSIONS
The product boric acid resulting from the reaction between borax particles and propiouic acid solution deposited on the
unreacted borax core. A 3-stage-control model based on spherical diffusion of the fluid reactant was developed for this
system. The rate controlling mechanism changed from chemical reaction in the early stage to diffusion through the boric
acid solid layer at the final stage of the process. Overall reaction between aqueous borax solution and oxalic acid crystals
resulted in precipitation of boric acid in the solution phase after complete dissolution of solid reactant. The method of
s-plane analysis was successfully used to determine the nucleation and growth rates of boric acid and the relative
nucleation kinetic correlation depicting the effect of significant process variables was established. In practice the
crystalline product may be produced by either one or combination of these two extreme cases.
NOTATION
B nucleation rate, no/kg water s
c normalized concenU'ationof propionic acid
cl normalized propionic acid concentration at R
c2 normalized propinnic acid concentration at rc
cA propionic acid concentration, tool/m3
Er relative activation energy, kJ/mol
G growth rate, m/s
k~ normalized rate constant for liquid film, kjTko
k~ normalized rate constant for ash layer diffusion, k.'/ko
k. rate constant for chemical reaction, k.'/ko
ko apparent rate constant, V/(4n zR2), m/s
L crystal size, ~m
L: mean crystal size at h, ~m
M~ molecular weight of borax
Mr magma density, kg crystal/kg free water
n population density, no/m kg water
N impeller speed, Hz
NA propiouic acid, mol
NA, moles of fluid in stoichiometric proportion with solid reactant, Wo/o M~
I~ universalgasconstant, 8.314 J/molK
R particle radius, m
ro unreacted core radius, m
s Laplace transform variable with respect to size, m"
t time, s
T temperature,°C, K
V solulion volume, m 3
W weight of species
W0 imtial weight of reactant crystals
W~ final or initial weight of species
X conversion of solid reactant
Greek letters
0 normalized time of a batch run
v normalized moles ofpropionic acid
~o normalized radius ofunreacted core
o moles of crystal reacting with one mole of the fluid reactant
z time for completion of reaction and batch, s
REFERENCES
Becket, P., 1983, Phosphates and Phosphoric Acid, Vol. M., Dekker publishers
Bowen, J.H., Khan, AR. and Mutasher, EI., 1989, Trans. Chem. Eng. Res. Des., 67, 58-65.
Doraiswamy, LK. and Sharma M M , 1984, Heterogeneous Reactions Analysis, Vol. II, John Wiley, New York.
Elnashaie, S.S., AI-Fariss, T.F., Abdel Razik, S,M. and Ibrahim, H.A., 1990, Ind. Eng. Chem. Res., 29, 2389-2401.
Levenspiel, O, 1972, Chemical reaction engineering, 2nd Edn., Wiley.
Sngimoto, r , 1987, Adv. in Colloid and Inter. Sci., 28, 65-108.
Tavare, N.S. and Garside J., 1990, Chem. Eng. Res. Des., 68, 115-122.
Tavare, N.S. and Garside, J., 1986, Chem. Eng. Res. Des., 64, 109-118.
Vander Sluis, S., Meszarns, Y., and Van Rosmalen, G.M, 1987, Ind. Eng. Chem. Res., 26, 2501-2505.
ZuckermanB., 1976, Photographic Science and Engineering, 20 (3), 111-116.